Novel Heterocyclic Alkanol Derivatives

ABSTRACT

The present invention relates to novel heterocyclic alkanol derivatives, to processes for preparing these compounds, to compositions comprising these compounds and to their use as biologically active compounds, in particular for controlling harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

The present invention relates to novel heterocyclic alkanol derivatives,to processes for preparing these compounds, to compositions comprisingthese compounds, and to the use thereof as biologically activecompounds, especially for control of harmful microorganisms in cropprotection and in the protection of materials and as plant growthregulators.

It is already known that particular heterocyclic alkanol derivatives canbe used in crop protection as fungicides and/or growth regulators (cf.EP-A 0 395 175, EP-A 0 409 418).

Since the ecological and economic demands made on modern activeingredients, for example fungicides, are increasing constantly, forexample with respect to activity spectrum, toxicity, selectivity,application rate, formation of residues and favourable manufacture, andthere can also be problems, for example, with resistances, there is aconstant need to develop novel fungicidal compositions which haveadvantages over the known compositions at least in some areas.

Novel heterocyclic alkanol derivatives of the formula (I)

have now been found, in which

-   X is O or S,-   Y is O, —CH₂— or a direct bond,-   m is 0 or 1,-   n is 0 or 1,-   R is in each case optionally substituted alkyl, alkenyl, cycloalkyl    or aryl,-   R¹ is hydrogen, SH, alkylthio, alkoxy, halogen, haloalkyl,    haloalkylthio, haloalkoxy, cyano, nitro or Si(alkyl)₃,-   A is in each case mono-Z-substituted phenyl or naphthyl,-   Z is halogen, cyano, nitro, OH, SH, C(alkyl)(═NOalkyl),    C₃-C₇-cycloalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,    C₂-C₄₋alkynyl, C₂-C₄-haloalkynyl, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl, formyl,    C₂-C₅-alkylcarbonyl, C₂-C₅-haloalkylcarbonyl, C₂-C₅-alkoxycarbonyl,    C₂-C₅-haloalkoxycarbonyl, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy,    C₂-C₅-alkylcarbonyloxy, C₂-C₅-haloalkylcarbonyloxy, trialkylsilyl,    or in each case optionally halogen-, C₁-C₄-allyl-, C₁-C₄-haloalkyl-,    C₁-C₄-alkoxy- or C₂-C₄-alkylcarbonyl-monosubstituted phenyl, phenoxy    or phenylthio,    and the agrochemically active salts thereof,    where A is not 4-chlorophenyl or 4-methylphenyl when Y is O, m is 0,    n is 0, R is t-butyl and R¹ is hydrogen.

The salts obtainable in this way likewise have fungicidal and/or plantgrowth-regulating properties.

The heterocyclic alkanol derivatives usable in accordance with theinvention are defined in general terms by the formula (I). Preferredradical definitions for the formulae specified above and below are givenbelow. These definitions apply equally to the end products of theformula (I) and to all intermediates (see also below under“Illustrations of the processes and intermediates”).

-   X is preferably S.-   X is likewise preferably O.-   Y is preferably O.-   Y is likewise preferably —CH₂—.-   Y is likewise preferably a direct bond.-   Y is more preferably O.-   Y is likewise more preferably —CH₂—.-   m is preferably 0.-   m is likewise preferably 1.-   n is preferably 0.-   n is likewise preferably 1.-   R is preferably in each case optionally branched C₃-C₇-alkyl,    C₁-C₈-haloalkyl, C₂-C₇-alkenyl, C₂-C₇-haloalkenyl, optionally    halogen-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-,    C₁-C₄-haloalkoxy-, C₁-C₄-haloalkylthio- or    C₁-C₄-alkylthio-substituted C₃-C₇-cycloalkyl, and optionally mono-    to tri-halogen- or —C₁-C₄-alkyl-substituted phenyl.-   R is more preferably in each case optionally branched C₃-C₅-alkyl,    C₁-C₆-haloalkyl, C₃-C₅-alkenyl, C₃-C₅-haloalkenyl, optionally    halogen-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-,    C₁-C₄-alkoxy-, C₁-C₄-haloalkylthio- or C₁-C₄-alkylthio-substituted    C₃-C₆-cycloalkyl.-   R is most preferably tert-butyl, isopropyl, 1-chlorocyclopropyl,    1-fluorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl,    1-methylthiocyclopropyl, 1-trifluoromethylcyclopropyl,    (3E)-4-chloro-2-methylbut-3-en-2-yl, C₁-C₄-haloalkyl.-   R¹ is preferably hydrogen, SH, C₁-C₄-alkoxy or halogen.-   R¹ is more preferably hydrogen, SH, methylthio, ethylthio, methoxy,    ethoxy, fluorine, chlorine, bromine or iodine.-   A is preferably mono-Z-substituted phenyl.-   A is more preferably 4-Z-substituted phenyl.-   A is likewise more preferably 2-Z-substituted phenyl.-   A is likewise more preferably 3-Z-substituted phenyl.-   A is preferably mono-Z-substituted naphthyl.-   A is more preferably mono-Z-substituted 1-naphthyl.-   A is likewise more preferably mono-Z-substituted 2-naphthyl.-   Z is preferably halogen, cyano, nitro,    C(C₁-C₅-allyl)(═NO(C₁-C₅-alkyl)), C₃-C₆-cycloalkyl, C₁-C₄-alkyl,    C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-alkynyl,    C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₂-C₅-alkylcarbonyl,    C₂-C₅-alkoxycarbonyl, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy,    C₂-C₅-alkylcarbonyloxy, or in each case optionally halogen-,    C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy- or    C₂-C₄-alkylcarbonyl-monosubstituted phenyl, phenoxy or phenylthio.-   Z is more preferably halogen, cyano, nitro,    C(C₁-C₄-alkyl)(═NO(C₁-C₄-alkyl)), C₃-C₆-cycloalkyl, C₁-C₄-alkyl,    C₁-C₂-haloalkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkoxy, C₁-C₂-alkylthio,    C₁-C₂-haloalkylthio, C₁-C₂-alkylsulphinyl, C₁-C₂-alkylsulphonyl,    acetyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, or in    each case optionally halogen-, C₁-C₂-alkyl-, C₁-C₂-haloalkyl-,    C₁-C₂-alkoxy-, acetyl-monosubstituted phenyl, phenoxy or phenylthio.-   Z is most preferably fluorine, chlorine, bromine, iodine, cyano,    nitro, CH(═NOMe), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,    methyl, ethyl, n-propyl, isopropyl, n-, s- or t-butyl,    trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl,    difluorochloromethyl, methoxy, trifluoromethoxy, difluoromethoxy,    methylthio, trifluoromethylthio, difluoromethylthio, or in each case    optionally fluorine-, chlorine-, bromine-, iodine-, methyl-, ethyl-,    trifluoromethyl-, trichloromethyl-, difluoromethyl-,    dichloromethyl-, difluorochloromethyl-, methoxy-,    acetyl-monosubstituted phenyl, phenoxy or phenylthio.

The radical definitions and explanations given above in general terms orstated within preferred ranges can, however, also be combined with oneanother as desired, i.e. including between the particular ranges andpreferred ranges. They apply both to the end products andcorrespondingly to precursors and intermediates. In addition, individualdefinitions may not apply.

Preference is given to those compounds of the formula (I) in which eachof the radicals have the above-mentioned preferred definitions.

Particular preference is given to those compounds of the formula (I) inwhich each of the radicals have the above-mentioned more preferreddefinitions.

Very particular preference is given to those compounds of the formula(I) in which each of the radicals have the abovementioned most preferreddefinitions.

Preference is also given to compounds of the formula (I) in which A is4-chlorophenyl, in which case Y is not O when m is 0, n is 0, R ist-butyl and R¹ is hydrogen.

Preference is also given to compounds of the formula (I) in which A is4-[(trifluoromethyl)sulphanyl]phenyl.

Preference is also given to compounds of the formula (I) in which A is4-bromophenyl.

Preference is also given to compounds of the formula (I) in which A is4-iodophenyl.

Preference is also given to compounds of the formula (I) in which A is2-fluorophenyl.

Preference is also given to compounds of the formula (I) in which A is4′-iodobiphenyl-4-yl.

Preference is also given to compounds of the formula (I) in which A is4-(trifluoromethoxy)phenyl.

Preference is also given to compounds of the formula (I) in which A is2-chlorophenyl.

Preference is also given to compounds of the formula (I) in which A is2-bromophenyl.

Preference is also given to compounds of the formula (I) in which A is3-iodophenyl.

Preference is also given to compounds of the formula (I) in which A is3-bromophenyl.

Preference is also given to compounds of the formula (I) in which A is3-nitrophenyl.

Preference is also given to compounds of the formula (I) in which A is4-tert-butylphenyl.

Preference is also given to compounds of the formula (I) in which A is4-phenoxyphenyl.

Preference is also given to compounds of the formula (I) in which A is4-fluorophenyl.

Preference is also given to compounds of the formula (I) in which A is4-chlorophenyl.

Preference is also given to compounds of the formula (I) in which A is4′-methoxybiphenyl-4-yl.

Preference is also given to compounds of the formula (I) in which A is4-cyclohexylphenyl.

Preference is also given to compounds of the formula (I) in which A is4-chlorophenoxy.

Preference is also given to compounds of the formula (I) in which A is4′-chlorobiphenyl-4-yl.

Preference is also given to compounds of the formula (I) in which A is4′-acetylbiphenyl-4-yl.

Preference is also given to compounds of the formula (I) in which A is4-[4-(trifluoromethyl)phenoxy]phenyl.

Preference is also given to compounds of the formula (I) in which A is4-[(E)-(methoxyimino)methyl]phenyl.

Preference is also given to compounds of the formula (I) in which A is4′-(trifluoromethyl)biphenyl-4-yl.

Preference is also given to compounds of the formula (I) in which A is4-(4-fluorophenoxy)phenyl.

Preference is also given to compounds of the formula (I) in which A is4-(4-chlorophenoxy)phenyl.

Preference is also given to compounds of the formula (I) in which A is4-(4-bromophenoxy)phenyl.

Preference is also given to compounds of the formula (I) in which A is3-phenoxyphenyl.

Preference is also given to compounds of the formula (I) in which Y isoxygen.

Preference is also given to compounds of the formula (I) in which Y is—CH₂—

Preference is also given to compounds of the formula (I) in which Y is adirect bond.

Preference is also given to compounds of the formula (I) in which R ist-butyl.

Preference is also given to compounds of the formula (I) in which R is1,3-difluoro-2-methylpropan-2-yl.

Preference is also given to compounds of the formula (I) in which R is1-methylcyclopropyl.

Preference is also given to compounds of the formula (I) in which R is1-fluorocyclopropyl.

Preference is also given to compounds of the formula (I) in which R is1-chlorocyclopropyl.

Preference is also given to compounds of the formula (I) in which R isisopropyl.

Preference is also given to compounds of the formula (I) in which R is1-methylcyclohexyl.

Preference is also given to compounds of the formula (I) in which n is0.

Preference is also given to compounds of the formula (I) in which n is1.

Preference is also given to compounds of the formula (I) in which m is1.

Preference is also given to compounds of the formula (I) in which X issulphur.

Preference is also given to compounds of the formula (I) in which R¹ ishydrogen.

Preference is also given to compounds of the formula (I) in which R¹ isSH.

Preference is also given to compounds of the formula (I) in which R¹ ischlorine.

The radical definitions specified above can be combined with one anotheras desired. In addition, individual definitions may not apply.

In the definitions of the symbols given in the above formulae,collective terms were used which are generally representative of thefollowing substituents:

halogen: (also in combinations such as haloalkyl, haloalkoxy etc.)fluorine, chlorine, bromine and iodine;alkyl: (including in combinations such as alkylthio, alkoxy etc.)saturated, straight-chain or branched hydrocarbyl radicals having 1 to 8carbon atoms, for example C₁-C₆-alkyl, such as methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl,pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; heptyl, octyl.Haloalkyl: (including in combinations such as haloalkylthio, haloalkoxyetc.) straight-chain or branched alkyl groups having 1 to 8 carbon atoms(as specified above), where some or all of the hydrogen atoms in thesegroups may be replaced by halogen atoms as specified above, for exampleC₁-C₃-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl,2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl.Alkenyl: unsaturated, straight-chain or branched hydrocarbyl radicalshaving 2 to 8 carbon atoms and one double bond in any position, forexample C₂-C₆-alkenyl such as ethenyl, 1-propenyl, 2-propenyl,1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl,2-methyl-1-butenyl, 3-methyl-1-butenyl, -methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl,3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.Cycloalkyl: monocyclic saturated hydrocarbyl groups having 3 to 8 carbonring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl.Aryl: unsubstituted or substituted, aromatic, mono-, bi- or tricyclicring, for example phenyl, naphthyl, anthracenyl (anthryl),phenanthracenyl (phenanthryl).Hetaryl: unsubstituted or substituted, unsaturated heterocyclic 5- to7-membered ring containing up to 4 nitrogen atoms or alternatively 1nitrogen atom and up to 2 further heteroatoms selected from N, O and S:for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl,3-pyrrolyl, 1-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,1-pyrazolyl, 1H-imidazol-4-yl, 1H-imidazol-5-yl, 1H-imidazol-1-yl,2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-yl, 1H-1,2,4-triazol-3-yl, 1H-1,2,4-triazol-5-yl,1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-3-yl, 4H-1,2,4-triazol-4-yl,1H-tetrazol-1-yl, 1H-tetrazol-5-yl, 2H-tetrazol-2-yl, 2H-tetrazol-5-yl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,3-thiadiazol-4-yl,1,2,3-thiadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,5-thiadiazol-3-yl,2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl,

Illustration of the Processes and Intermediates

The heterocyclic alkanol derivatives of the formula (I) can be preparedin different ways (cf. EP-A 0 409 418). First of all, the possibleprocesses are shown schematically below. Unless indicated otherwise, theradicals specified are each as defined above.

Preferred radical definitions for the formulae and schemes above andbelow have already been given above. These definitions apply not only tothe end products of the formula (I) but likewise to all intermediates.

Process A

Some of the compounds of the formula (II) required as starting materialsin the performance of process A according to the invention are known.They can be prepared in a known manner (cf. Z. Anorg. Allg. Chem. 2001,627, 2408-2412).

The ketones of the formula (III) also required as starting materials forprocess A according to the invention are known (cf. EP-A 0 409 418).

Process A according to the invention is typically performed in thepresence of a diluent, e.g. diethyl ether, tetrahydrofuran ordichloromethane, at temperatures of −80° C. to +80° C. The resultingproduct is scavenged with a proton donor.

The inventive reaction is preferably performed under inert gas such asespecially nitrogen or argon.

Process B

Some of the ketones of the formula (IV) required as starting materialsin the performance of process B according to the invention are known.They can be prepared in a known manner (cf. EP-A 0 409 418).

The organometallic heterocycles of the formula (V) also required asstarting materials for process B according to the invention are known(cf. EP-A 0 409 418 and EP-A 0 395 175).

In the case of preparation of organometallic heterocycles of the formula(V), it may be advantageous to provide the 2 position with a suitableprotecting group, e.g. trimethylsilyl, in order to direct M² into the 5position. This protecting group can, but need not, be detached beforethe reaction with the ketones of the formula (IV).

Process B according to the invention is typically performed in thepresence of a diluent, e.g. tetrahydrofuran or diethyl ether, attemperatures of −120° C. to +80° C. The resulting product is scavengedwith a proton donor.

The inventive reaction is preferably performed under inert gas such asespecially nitrogen or argon.

Process C

The compounds of the formula (VII) required as starting materials in theperformance of process C according to the invention are known.

Some of the oxirane derivatives of the formula (VIII) also required asstarting materials of process C according to the invention are known.

Novel oxirane derivatives are those of the formula (VIII-a)

in which

-   X is as defined above,-   R^(a) is in each case optionally substituted alkyl (excluding    tert-butyl when X is S), alkenyl, cycloalkyl or aryl.-   R^(a) is preferably in each case optionally branched C₃-C₇-alkyl    (excluding tert-butyl when X is S), C₁-C₈-haloalkyl, C₂-C₇-alkenyl,    C₂-C₇-haloalkenyl, optionally halogen-, C₁-C₄-alkyl-,    C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-,    C₁-C₄-haloalkylthio- or C₁-C₄-alkylthio-substituted    C₃-C₇-cycloalkyl, and optionally mono- to tri-halogen- or    —C₁-C₄-alkyl-substituted phenyl.-   R^(a) is more preferably in each case optionally branched    C₃-C₅-alkyl excluding tert-butyl, C₁-C₆-haloalkyl, C₃-C₅-alkenyl,    C₃-C₅-haloalkenyl, optionally halogen-, C₁-C₄-alkyl-,    C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-,    C₁-C₄-haloalkylthio- or C₁-C₄-alkylthio-substituted    C₃-C₆-cycloalkyl.-   R^(a) is most preferably isopropyl, 1-chlorocyclopropyl,    1-fluorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl,    1-methylthiocyclopropyl, (3E)-4-chloro-2-methylbut-3-en-2-yl,    C₁-C₄-haloalkyl.

Novel oxirane derivatives of the formula (VIII-a) likewise form part ofthe subject-matter of this invention. Process C according to theinvention is performed in the presence of a diluent, for exampleN,N-dimethylformamide, and optionally in the presence of a base, forexample sodium hydride or potassium carbonate.

Process D

Some of the oxirane derivatives of the formula (IX) required as startingmaterials in the performance of process D according to the invention areknown (cf. EP-A 0 121 171).

2-Chloro-1,3-thiazole of the formula (X) is known.

For conversion of DC, it is possible to use organometallic compounds,especially alkyllithium compounds (e.g. n-butyllithium) (cf. EP-A 0 395175).

Process D according to the invention is typically performed in thepresence of a diluent, for example tetrahydrofuran or diethyl ether, attemperatures of −120° C. to +80° C. The resulting product is scavengedwith a proton donor. The inventive reaction is preferably performedunder inert gas such as especially nitrogen or argon.

Process E

The compounds of the formula (I-d) preparable in the abovementionedprocesses can be converted further to the target compounds of thegeneral structure (I-e).

For conversion of compounds of the formula (I-d), it is possible to useorganometallic compounds, especially alkyllithium compounds (e.g.n-butyllithium) (cf. EP-A 0 906 292).

The organometallic compound which forms as an intermediate is typicallyreacted with an electrophile (e.g. sulphur, alkyl halide, interhalogencompound) to give the target compound (I-e).

Process E according to the invention is typically performed in thepresence of a diluent, for example tetrahydrofuran or diethyl ether, attemperatures of −120° C. to +80° C. The resulting product is scavengedwith a proton donor. The inventive reaction is preferably performedunder inert gas such as especially nitrogen or argon.

Process F

The compounds of the formula (I-f) preparable in the abovementionedprocesses can be converted further to the target compounds of thegeneral structure (I-d).

For conversion of compounds of the formula (I-f), it is possible to usemetals, preferably zinc (cf. EP-A 0 395 175).

Process F according to the invention is typically performed in thepresence of a diluent, for example tetrahydrofuran or else organicacids, for example acetic acid, at temperatures of −120° C. to +150° C.

The inventive heterocyclic alkanol derivatives of the general formula(I) can be converted to acid addition salts or metal salt complexes.

For preparation of physiologically acceptable acid addition salts of thecompounds of the general formula (I), the following acids are preferredoptions: hydrohalic acids, for example hydrochloric acid and hydrobromicacid, especially hydrochloric acid, and also phosphoric acid, nitricacid, sulphuric acid, mono- and bifunctional carboxylic acids andhydroxycarboxylic acids, for example acetic acid, maleic acid, succinicacid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbicacid, lactic acid, and sulphonic acids, for example p-toluenesulphonicacid and 1,5-naphthalenedisulphonic acid.

The acid addition salts of the compounds of the general formula (I) canbe obtained in a simple manner by customary methods for forming salts,for example by dissolving a compound of the general formula (I) in asuitable inert solvent and adding the acid, for example hydrochloricacid, and can be isolated in a known manner, for example by filteringthem off, and can optionally be purified by washing with an inertorganic solvent.

For preparation of metal salt complexes of the compounds of the generalformula (I), preferred options are salts of metals of main group II toIV and of transition groups I and II and IV to VIII of the PeriodicTable, examples of which include copper, zinc, manganese, magnesium,tin, iron and nickel.

Useful anions of the salts include those which are preferably derivedfrom the following acids: hydrohalic acids, for example hydrochloricacid and hydrobromic acid, and also phosphoric acid, nitric acid andsulphuric acid.

The metal salt complexes of compounds of the general formula (I) can beobtained in a simple manner by customary processes, for example bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to the compound of the general formula I. Metal saltcomplexes can be isolated in a known manner, for example by filteringthem off, and can optionally be purified by recrystallization.

The present invention further relates to a crop protection compositionfor controlling unwanted microorganisms, especially unwanted fungi,comprising the inventive active ingredients. These are preferablyfungicidal compositions which comprise agriculturally suitableauxiliaries, solvents, carriers, surfactants or extenders.

The invention also relates to a method for controlling unwantedmicroorganisms, characterized in that the inventive active ingredientsare applied to the phytopathogenic fungi and/or their habitat.

According to the invention, a carrier is a natural or synthetic, organicor inorganic substance with which the active ingredients are mixed orcombined for better applicability, in particular for application toplants or plant parts or seed. The carrier, which may be solid orliquid, is generally inert and should be suitable for use inagriculture.

Useful solid or liquid carriers include: for example ammonium salts andnatural rock dusts, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and synthetic rockdusts, such as finely divided silica, alumina and natural or syntheticsilicates, resins, waxes, solid fertilizers, water, alcohols, especiallybutanol, organic solvents, mineral and vegetable oils, and derivativesthereof. Mixtures of such carriers can likewise be used. Useful solidcarriers for granules include: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite, dolomite, andsynthetic granules of inorganic and organic meals, and also granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks.

Useful liquefied gaseous extenders or carriers are those liquids whichare gaseous at standard temperature and under standard pressure, forexample aerosol propellants such as halohydrocarbons, and also butane,propane, nitrogen and carbon dioxide.

In the formulations, it is possible to use tackifiers such ascarboxymethylcellulose, and natural and synthetic polymers in the formof powders, granules or latices, such as gum arabic, polyvinyl alcoholand polyvinyl acetate, or else natural phospholipids such as cephalinsand lecithins and synthetic phospholipids. Further additives may bemineral and vegetable oils.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Useful liquid solvents areessentially: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or dichloromethane, aliphatichydrocarbons such as cyclohexane or paraffins, for example mineral oilfractions, mineral and vegetable oils, alcohols such as butanol orglycol and their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

The inventive compositions may additionally comprise further components,for example surfactants. Useful surfactants are emulsifiers and/or foamformers, dispersants or wetting agents having ionic or nonionicproperties, or mixtures of these surfactants. Examples of these aresalts of polyacrylic acid, salts of lignosulphonic acid, salts ofphenolsulphonic acid or naphthalenesulphonic acid, polycondensates ofethylene oxide with fatty alcohols or with fatty acids or with fattyamines, substituted phenols (preferably alkylphenols or arylphenols),salts of sulphosuccinic esters, taurine derivatives (preferably alkyltaurates), phosphoric esters of polyethoxylated alcohols or phenols,fatty esters of polyols, and derivatives of the compounds containingsulphates, sulphonates and phosphates, for example alkylaryl polyglycolethers, alkylsulphonates, alkylsulphates, arylsulphonates, proteinhydrolysates, lignosulphite waste liquors and methylcellulose. Thepresence of a surfactant is necessary if one of the active ingredientsand/or one of the inert carriers is insoluble in water and whenapplication is effected in water. The proportion of surfactants isbetween 5 and 40 percent by weight of the inventive composition.

It is possible to use dyes such as inorganic pigments, for example ironoxide, titanium oxide and Prussian Blue, and organic dyes such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

If appropriate, it is also possible for other additional components tobe present, for example protective colloids, binders, adhesives,thickeners, thixotropic substances, penetrants, stabilizers,sequestrants, complexing agents. In general, the active ingredients canbe combined with any solid or liquid additive commonly used forformulation purposes.

The inventive compositions and formulations generally contain between0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1and 95% by weight, more preferably between 0.5 and 90% of activeingredient, most preferably between 10 and 70% by weight.

The inventive active ingredients or compositions can be used as such or,depending on their particular physical and/or chemical properties, inthe form of their formulations or the use forms prepared therefrom, suchas aerosols, capsule suspensions, cold-fogging concentrates,warm-fogging concentrates, encapsulated granules, fine granules,flowable concentrates for the treatment of seed, ready-to-use solutions,dustable powders, emulsifiable concentrates, oil-in-water emulsions,water-in-oil emulsions, macrogranules, microgranules, oil-dispersiblepowders, oil-miscible flowable concentrates, oil-miscible liquids,foams, pastes, pesticide coated seed, suspension concentrates,suspoemulsion concentrates, soluble concentrates, suspensions, wettablepowders, soluble powders, dusts and granules, water-soluble granules ortablets, water-soluble powders for the treatment of seed, wettablepowders, natural products and synthetic substances impregnated withactive ingredient, and also microencapsulations in polymeric substancesand in coating materials for seed, and also ULV cold-fogging andwarm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active ingredients with at least one customaryextender, solvent or diluent, emulsifier, dispersant, and/or binder orfixative, wetting agent, water repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, antifoams,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The inventive compositions include not only formulations which arealready ready for use and can be applied with a suitable apparatus tothe plant or the seed, but also commercial concentrates which have to bediluted with water prior to use.

The inventive active ingredients may be present as such or in their(commercial) formulations and in the use forms prepared from theseformulations as a mixture with other (known) active ingredients, such asinsecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The inventive treatment of the plants and plant parts with the activeingredients or compositions is effected directly or by action on theirsurroundings, habitat or storage space by the customary treatmentmethods, for example by dipping, spraying, atomizing, irrigating,evaporating, dusting, fogging, broadcasting, foaming, painting,spreading-on, watering (drenching), drip irrigating and, in the case ofpropagation material, especially in the case of seeds, also by dry seedtreatment, wet seed treatment, slurry treatment, incrustation, coatingwith one or more coats, etc. It is also possible to deploy the activeingredients by the ultra-low volume method or to inject the activeingredient preparation/the active ingredient itself into the soil.

The invention further comprises a method for treating seed.

The invention further relates to seed which has been treated by one ofthe methods described in the previous paragraph. The inventive seeds areemployed in methods for the protection of seed from unwantedmicroorganisms. In these methods, seed treated with at least oneinventive active ingredient is used.

The inventive active ingredients or compositions are also suitable fortreating seed. A large part of the damage to crop plants caused byharmful organisms is triggered by the infection of the seed duringstorage or after sowing, and also during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even minor damage mayresult in the death of the plant. There is therefore a great interest inprotecting the seed and the germinating plant by using appropriatecompositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of constant improvements.However, the treatment of seed entails a series of problems which cannotalways be solved in a satisfactory manner. For instance, it is desirableto develop methods for protecting the seed and the germinating plant,which dispense with, or at least significantly reduce, the additionaldeployment of crop protection compositions after planting or afteremergence of the plants. It is also desirable to optimize the amount ofthe active ingredient used so as to provide the best possible protectionfor the seed and the germinating plant from attack by phytopathogenicfungi, but without damaging the plant itself by the active ingredientemployed. In particular, methods for the treatment of seed should alsotake account of the intrinsic fungicidal properties of transgenic plantsin order to achieve optimal protection of the seed and the germinatingplant with a minimum expenditure of crop protection compositions.

The present invention therefore also relates to a method for protectionof seed and germinating plants from attack by phytopathogenic fungi, bytreating the seed with an inventive composition. The invention likewiserelates to the use of the inventive compositions for treatment of seedto protect the seed and the germinating plant from phytopathogenicfungi. The invention further relates to seed which has been treated withan inventive composition for protection from phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis effected primarily by treating the soil and the above-ground parts ofplants with crop protection compositions. Owing to the concernsregarding a possible influence of the crop protection compositions onthe environment and the health of humans and animals, there are effortsto reduce the amount of active ingredients deployed.

One of the advantages of the present invention is that the particularsystemic properties of the inventive active ingredients and compositionsmean that treatment of the seed with these active ingredients andcompositions not only protects the seed itself, but also the resultingplants after emergence, from phytopathogenic fungi. In this way, theimmediate treatment of the crop at the time of sowing or shortlythereafter can be dispensed with.

It is likewise considered to be advantageous that the inventive activeingredients or compositions can especially also be used with transgenicseed, in which case the plant growing from this seed is capable ofexpressing a protein which acts against pests. By virtue of thetreatment of such seed with the inventive active ingredients orcompositions, merely the expression of the protein, for example aninsecticidal protein, can control certain pests. Surprisingly, a furthersynergistic effect can be observed in this case, which additionallyincreases the effectiveness for protection against attack by pests.

The inventive compositions are suitable for protecting seed of any plantvariety which is used in agriculture, in greenhouses, in forests or inhorticulture and viticulture. In particular, this is the seed of cereals(such as wheat, barley, rye, triticale, sorghum/millet and oats), maize,cotton, soya beans, rice, potatoes, sunflower, bean, coffee, beet (forexample sugar beet and fodder beet), peanut, oilseed rape, poppy, olive,coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato,cucumbers, onions and lettuce), turf and ornamentals (see also below).The treatment of the seed of cereals (such as wheat, barley, rye,triticale and oats), main and rice is of particular significance.

As also described below, the treatment of transgenic seed with theinventive active ingredients or compositions is of particularsignificance. This relates to the seed of plants containing at least oneheterologous gene which enables the expression of a polypeptide orprotein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. This heterologous gene preferablyoriginates from Bacillus sp., in which case the gene product iseffective against the European maize borer and/or the Western maizerootworm. The heterologous gene more preferably originates from Bacillusthuringiensis.

In the context of the present invention, the inventive composition isapplied to the seed alone or in a suitable formulation. Preferably, theseed is treated in a state in which it is sufficiently stable for nodamage to occur in the course of treatment. In general, the seed can betreated at any time between harvest and sowing. It is customary to useseed which has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. For example, itis possible to use seed which has been harvested, cleaned and dried downto a moisture content of less than 15% by weight. Alternatively, it isalso possible to use seed which, after drying, for example, has beentreated with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe inventive composition applied to the seed and/or the amount offurther additives is selected such that the germination of the seed isnot impaired, or that the resulting plant is not damaged. This has to beborne in mind in particular in the case of active ingredients which canhave phytotoxic effects at certain application rates.

The inventive compositions can be applied directly, i.e. withoutcontaining any other components and without having been diluted. Ingeneral, it is preferable to apply the compositions to the seed in theform of a suitable formulation. Suitable formulations and methods forseed treatment are known to those skilled in the art and are described,for example, in the following documents: U.S. Pat. No. 4,272,417, U.S.Pat. No. 4,245,432, U.S. Pat. No. 4,808,430, U.S. Pat. No. 5,876,739, US2003/0176428 A 1, WO 2002/080675, WO 2002/028186.

The active ingredients usable in accordance with the invention can beconverted to the customary seed dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing the activeingredients with customary additives, for example customary extendersand also solvents or diluents, dyes, wetting agents, dispersants,emulsifiers, antifoams, preservatives, secondary thickeners, adhesives,gibberellins and also water.

Useful dyes which may be present in the seed dressing formulationsusable in accordance with the invention are all dyes which are customaryfor such purposes. It is possible to use either pigments, which aresparingly soluble in water, or dyes, which are soluble in water.Examples include the dyes known by the names Rhodamine B, C.I. PigmentRed 112 and C.I. Solvent Red 1.

Useful wetting agents which may be present in the seed dressingformulations usable in accordance with the invention are all substanceswhich promote wetting and which are conventionally used for theformulation of active agrochemical ingredients. Preference is given tousing alkyl naphthalenesulphonates, such as diisopropyl or diisobutylnaphthalenesulphonates.

Useful dispersants and/or emulsifiers which may be present in the seeddressing formulations usable in accordance with the invention are allnonionic, anionic and cationic dispersants conventionally used for theformulation of active agrochemical ingredients. Usable with preferenceare nonionic or anionic dispersants or mixtures of nonionic or anionicdispersants. Suitable nonionic dispersants include especially ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and the phosphated or sulphatedderivatives thereof. Suitable anionic dispersants are especiallylignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed dressing formulations usablein accordance with the invention are all foam-inhibiting substancesconventionally used for the formulation of active agrochemicalingredients. Silicone antifoams and magnesium stearate can be used withpreference.

Preservatives which may be present in the seed dressing formulationsusable in accordance with the invention are all substances usable forsuch purposes in agrochemical compositions. Examples includedichlorophene and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed dressingformulations usable in accordance with the invention are all substancesusable for such purposes in agrochemical compositions. Preferredexamples include cellulose derivatives, acrylic acid derivatives,xanthan, modified clays and finely divided silica.

Adhesives which may be present in the seed dressing formulations usablein accordance with the invention are all customary binders usable inseed dressing products. Preferred examples include polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose.

The gibberellins which may be present in the seed dressing formulationsusable in accordance with the invention may preferably be gibberellinsA1, A3 (=gibberellic acid), A4 and A7; particular preference is given tousing gibberellic acid. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel” [Chemistryof the Crop Protection Compositions and Pesticides), vol. 2, SpringerVerlag, 1970, p. 401-412).

The seed dressing formulations usable in accordance with the inventioncan be used, either directly or after previously having been dilutedwith water, for the treatment of a wide range of different seed,including the seed of transgenic plants. In this case, additionalsynergistic effects may also occur in interaction with the substancesformed by expression.

For treatment of seed with the seed dressing formulations usable inaccordance with the invention, or the preparations prepared therefrom byadding water, all mixing units usable customarily for the seed dressingare useful. Specifically, the procedure in the seed dressing is to placethe seed into a mixer, to add the particular desired amount of seeddressing formulations, either as such or after prior dilution withwater, and to mix everything until the formulation is distributedhomogeneously on the seed. If appropriate, this is followed by a dryingoperation.

The inventive active ingredients or compositions have potentmicrobicidal activity and can be used for control of unwantedmicroorganisms, such as fungi and bacteria, in crop protection and inthe protection of materials.

Fungicides can be used in crop protection for control ofPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection for control ofPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

The inventive fungicidal compositions can be used for curative orprotective control of phytopathogenic fungi. The invention thereforealso relates to curative and protective methods for controllingphytopathogenic fungi by the use of the inventive active ingredients orcompositions, which are applied to the seed, the plant or plant parts,the fruit or the soil in which the plants grow.

The inventive compositions for controlling phytopathogenic fungi in cropprotection comprise an effective but non-phytotoxic amount of theinventive active ingredients. An “effective but non-phytotoxic amount”means an amount of the inventive composition which is sufficient tocontrol the fungal disease of the plant in a satisfactory manner or toeradicate the fungal disease completely, and which, at the same time,does not cause any significant symptoms of phytotoxicity. In general,this application rate may vary within a relatively wide range. Itdepends on several factors, for example on the fungus to be controlled,the plant, the climatic conditions and the ingredients of the inventivecompositions.

The fact that the active ingredients are well tolerated by plants at theconcentrations required for controlling plant diseases allows thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

All plants and plant parts can be treated in accordance with theinvention. Plants are understood here to mean all plants and plantpopulations, such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants may be plantswhich can be obtained by conventional breeding and optimization methodsor by biotechnological and genetic engineering methods or combinationsof these methods, including the transgenic plants and including theplant varieties which are protectable and non-protectable by plantbreeders' rights. Plant parts are understood to mean all parts andorgans of plants above and below the ground, such as shoot, leaf, flowerand root, examples of which include leaves, needles, stalks, stems,flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. Partsof plants also include harvested material and vegetative and generativepropagation material, for example seedlings, tubers, rhizomes, cuttingsand seeds.

The inventive active ingredients, when they are well tolerated byplants, have favourable homeotherm toxicity and are well tolerated bythe environment, are suitable for protecting plants and plant organs,for enhancing harvest yields, for improving the quality of the harvestedmaterial. They can preferably be used as crop protection compositions.They are active against normally sensitive and resistant species andagainst all or some stages of development.

Plants which can be treated in accordance with the invention include thefollowing: cotton, flax, grapevine, fruit, vegetables, such as Rosaceaesp. (for example pome fruits such as apples and pears, but also stonefruits such as apricots, cherries, almonds and peaches, and soft fruitssuch as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceaesp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp.,Actimidaceae sp., Lauraceae sp., Musaceae sp. (for example banana plantsand banana plantations), Rubiaceae sp. (for example coffee), Theaceaesp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges andgrapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp.,Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp.,Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceaesp. (for example leeks, onions), Papilionaceae sp. (for example peas);major crop plants such as Gramineae sp. (for example maize, turf,cereals such as wheat, rye, rice, barley, oats, millet and triticale),Poaceae sp. (for example sugar cane), Asteraceae sp. (for examplesunflower), Brassicaceae sp. (for example white cabbage, red cabbage,broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes,and also oilseed rape, mustard, horseradish and cress), Fahacae sp. (forexample beans, peanuts), Papilionaceae sp. (for example soya beans),Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for examplesugar beet, fodder beet, Swiss chard, beetroot); useful plants andornamental plants in gardens and forests; and genetically modified typesof each of these plants.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andalso parts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineering,if appropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above. Morepreferably, plants of the plant cultivars which are each commerciallyavailable or in use are treated in accordance with the invention. Plantcultivars are understood to mean plants which have new properties(“traits”) and have been obtained by conventional breeding, bymutagenesis or by recombinant DNA techniques. They can be cultivars,varieties, bio- or genotypes.

The inventive treatment method can be used for the treatment ofgenetically modified organisms (GMOs), for example plants or seeds.Genetically modified plants (or transgenic plants) are plants in which aheterologous gene has been integrated stably into the genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAi technology [RNAinterference]). A heterologous gene present in the genome is also calleda transgene. A transgene that is defined by its specific presence in theplant genome is called a transformation or transgenic event.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. For example, the following effects exceedingthe effects actually to be expected are possible: reduced applicationrates and/or a widening of the activity spectrum and/or an increase inthe activity of the active ingredients and compositions which can beused according to the invention, better plant growth, increasedtolerance to high or low temperatures, increased tolerance to drought orto water or soil salt content, increased flowering performance, easierharvesting, accelerated maturation, higher harvest yields, biggerfruits, larger plant height, greener leaf colour, earlier flowering,higher quality and/or a higher nutritional value of the harvestedproducts, higher sugar concentration within the fruits, better storagestability and/or processibility of the harvested products.

At certain application rates, the inventive active ingredients may alsohave a fortifying effect on plants. They are therefore suitable formobilizing the defence system of the plant against attack by unwantedphytopathogenic fungi and/or microorganisms and/or viruses. This may beone of the reasons for the enhanced activity of the inventivecombinations, for example against fungi. Plant-fortifying(resistance-inducing) substances shall be understood to mean, in thepresent context, also those substances or combinations of substanceswhich are capable of stimulating the defence system of plants in such away that, when subsequently inoculated with unwanted phytopathogenicfungi, the plants treated display a substantial degree of resistance tothese unwanted phytopathogenic fungi. The inventive substances cantherefore be used for protection of plants from attack by the pathogensmentioned within a certain period of time after the treatment. Theperiod within which protection is achieved generally extends for from 1to 10 days, preferably 1 to 7 days, after the treatment of the plantswith the active ingredients.

Plants and plant varieties which are preferably treated in accordancewith the invention include all plants which have genetic material whichimparts particularly advantageous, useful traits to these plants(whether obtained by breeding and/or biotechnological means).

Plants and plant varieties which are likewise preferably treated inaccordance with the invention are resistant to one or more biotic stressfactors, i.e. said plants have a better defence against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstress factors. Abiotic stress conditions may include, for example,drought, cold temperature exposure, heat exposure, osmotic stress,waterlogging, increased soil salinity, increased exposure to minerals,exposure to ozone, exposure to strong light, limited availability ofnitrogen nutrients, limited availability of phosphorus nutrients orshade avoidance.

Plants and plant varieties which can likewise be treated in accordancewith the invention are those plants which are characterized by enhancedyield characteristics. Enhanced yield in these plants may be the resultof, for example, improved plant physiology, improved plant growth anddevelopment, such as water use efficiency, water retention efficiency,improved nitrogen use, enhanced carbon assimilation, improvedphotosynthesis, increased germination efficiency and acceleratedmaturation. Yield can also be affected by improved plant architecture(under stress and non-stress conditions), including early flowering,flowering control for hybrid seed production, seedling vigour, plantsize, internode number and distance, root growth, seed size, fruit size,pod size, pod or ear number, seed number per pod or ear, seed mass,enhanced seed filling, reduced seed dispersal, reduced pod dehiscenceand lodging resistance. Further yield traits include seed composition,such as carbohydrate content, protein content, oil content andcomposition, nutritional value, reduction in anti-nutritional compounds,improved processibility and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid effect,which results in generally higher yield, vigour, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallyproduced by crossing an inbred male-sterile parent line (the femaleparent) with another inbred male-fertile parent line (the male parent).The hybrid seed is typically harvested from the male-sterile plants andsold to growers. Male-sterile plants can sometimes (for example inmaize) be produced by detasseling (i.e. mechanical removal of the malereproductive organs or male flowers); however, it is more typical formale sterility to be the result of genetic determinants in the plantgenome. In that case, and especially when seed is the desired product tobe harvested from the hybrid plants, it is typically beneficial toensure that male fertility in hybrid plants, which contain the geneticdeterminants responsible for male sterility, is fully restored. This canbe accomplished by ensuring that the male parents have appropriatefertility restorer genes which are capable of restoring the malefertility in hybrid plants that contain the genetic determinantsresponsible for male sterility. Genetic determinants for male sterilitymay be located in the cytoplasm. Examples of cytoplasmic male sterility(CMS) were for instance described for Brassica species. However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male-sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396, in which, forexample, a ribonuclease such as a bamase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are, for example, glyphosate-tolerant plants,i.e. plants which have been made tolerant to the herbicide glyphosate orsalts thereof. For example, glyphosate-tolerant plants can be obtainedby transforming the plant with a gene which encodes the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants that have beenmade tolerant to herbicides inhibiting the enzyme glutamine synthase,such as bialaphos, phosphinothricin or glufosinate. Such plants can beobtained by expressing an enzyme detoxifying the herbicide or a mutantglutamine synthase enzyme that is resistant to inhibition. One suchefficient detoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase have been described.

Further herbicide-tolerant plants are also plants that have been madetolerant to the herbicides inhibiting the enzymehydroxyphenylpyruvatedioxygenase (1-IPPD).Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse the reactionin which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate.Plants tolerant to HPPD inhibitors can be transformed with a geneencoding a naturally occurring resistant HPPD enzyme, or a gene encodinga mutated HPPD enzyme. Tolerance to HPPD inhibitors can also be obtainedby transforming plants with genes encoding certain enzymes enabling theformation of homogentisate despite the inhibition of the native HPPDenzyme by the HPPD inhibitor. Tolerance of plants to HPPD inhibitors canalso be improved by transforming plants with a gene encoding an enzymeprephenate dehydrogenase in addition to a gene encoding an HPPD-tolerantenzyme.

Further herbicide-resistant plants are plants that have been madetolerant to acetolactate synthase (ALS) inhibitors. The known ALSinhibitors include, for example, sulphonylurea, imidazolinone,triazolopyrimidines, pyrimidinyl oxy(thio)benzoates and/orsulphonylaminocarbonyltriazolinone herbicides. Different mutations inthe ALS enzyme (also known as acetohydroxy acid synthase, AHAS) areknown to confer tolerance to different herbicides and groups ofherbicides. The production of sulphonylurea-tolerant plants andimidazolinone-tolerant plants has been described in the internationalpublication WO 1996/033270. Further sulphonylurea- andimidazolinone-tolerant plants have also been described, for example inWO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, by selection in cell cultures in thepresence of the herbicide or by mutation breeding.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation which imparts such insect resistance.

In the present context, the term “insect-resistant transgenic plant”includes any plant containing at least one transgene comprising a codingsequence encoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins compiled online at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or    insecticidal portions thereof, for example proteins of the Cry    protein classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or    insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein than Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy3Ae and Cy3Bb crystal    proteins; or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, for example the Cry1A.105 protein produced by maize event    MON98034 (WO 2007/027777); or-   4) a protein of any one of points 1) to 3) above wherein some,    particularly 1 to 10, amino acids have been replaced by another    amino acid to obtain a higher insecticidal activity to a target    insect species, and/or to expand the range of target insect species    affected, and/or because of changes induced in the encoding DNA    during cloning or transformation, such as the Cry3Bb1 protein in    maize events MON863 or MON88017, or the Cry3A protein in maize event    MIR604; or-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal proteins (VIP) listed at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html, for    example proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP 1A and VIP2A proteins;-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of points 1) to 3) above wherein some,    particularly 1 to 10, amino acids have been replaced by another    amino acid to obtain a higher insecticidal activity to a target    insect species, and/or to expand the range of target insect species    affected, and/or because of changes induced in the encoding DNA    during cloning or transformation (while still encoding an    insecticidal protein), such as the VIP3Aa protein in cotton event    COT 102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the abovementioned classes 1 to 8. In oneembodiment, an insect-resistant plant contains more than one transgeneencoding a protein of any one of the abovementioned classes 1 to 8, toexpand the range of target insect species affected or to delay insectresistance development to the plants, by using different proteinsinsecticidal to the same target insect species but having a differentmode of action, such as binding to different receptor binding sites inthe insect.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stress factors. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such stress resistance. Particularly usefulstress-tolerant plants include the following:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants;-   b. plants which contain a stress tolerance-enhancing transgene    capable of reducing the expression and/or the activity of the    PARG-encoding genes of the plants or plant cells;-   c. plants which contain a stress tolerance-enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyltransferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   1) Transgenic plants which synthesize a modified starch which is    altered with respect to its chemophysical traits, in particular the    amylose content or the amylose/amylopectin ratio, the degree of    branching, the average chain length, the distribution of the side    chains, the viscosity behaviour, the gel resistance, the grain size    and/or grain morphology of the starch in comparison to the    synthesized starch in wild-type plant cells or plants, such that    this modified starch is better suited for certain applications.-   2) Transgenic plants which synthesize non-starch carbohydrate    polymers or which synthesize non-starch carbohydrate polymers with    altered properties in comparison to wild-type plants without genetic    modification. Examples are plants which produce polyfructose,    especially of the inulin and levan type, plants which produce    alpha-1,4-glucans, plants which produce alpha-1,6-branched    alpha-1,4-glucans, and plants producing alternan.-   3) Transgenic plants which produce hyaluronan.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

-   a) plants, such as cotton plants, which contain an altered form of    cellulose synthase genes;-   b) plants, such as cotton plants, which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fibre cell is altered, for    example through downregulation of fibre-selective β-1,3-glucanase;-   f) plants, such as cotton plants, which have fibres with altered    reactivity, for example through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation, or by selection of plants containing a mutationimparting such altered oil characteristics and include:

-   a) plants, such as oilseed rape plants, which produce oil having a    high oleic acid content;-   b) plants, such as oilseed rape plants, which produce oil having a    low linolenic acid content;-   c) plants, such as oilseed rape plants, which produce oil having a    low level of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins are the transgenic plants which are sold under thefollowing trade names: YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), BiteGard® (for example maize),BT-Xtra® (for example maize), StarLink® (for example maize), Bollgard®(cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (forexample maize), Protecta® and NewLeaf® (potato). Examples ofherbicide-tolerant plants which should be mentioned are maize varieties,cotton varieties and soya bean varieties which are available under thefollowing trade names: Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya beans), Liberty Link® (tolerance tophosphinothricin, for example oilseed rape), IMI® (tolerance toimidazolinone) and SCS (tolerance to sulphonylurea, for example maize).Herbicideresistant plants (plants bred in a conventional manner forherbicide tolerance) which should be mentioned include the varietiessold under the Clearfield® name (for example maize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing trans-formation events, or acombination of transformation events, and that are listed for example inthe databases for various national or regional regulatory agencies (seefor example http://gmoinfojrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The inventive active ingredients or compositions can also be used in theprotection of materials, for protection of industrial materials againstattack and destruction by unwanted microorganisms, for example fungi andinsects.

In addition, the inventive compounds can be used as antifoulingcompositions, alone or in combinations with other active ingredients.

Industrial materials in the present context are understood to meaninanimate materials which have been prepared for use in industry. Forexample, industrial materials which are to be protected by inventiveactive ingredients from microbial alteration or destruction may beadhesives, sizes, paper, wallpaper and board, textiles, carpets,leather, wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with or destroyed by microorganisms.Parts of production plants and buildings, for example cooling-watercircuits, cooling and heating systems and ventilation andair-conditioning units, which may be impaired by the proliferation ofmicroorganisms may also be mentioned within the scope of the materialsto be protected. Industrial materials within the scope of the presentinvention preferably include adhesives, sizes, paper and card, leather,wood, paints, cooling lubricants and heat transfer fluids, morepreferably wood. The inventive active ingredients or compositions mayprevent adverse effects, such as rotting, decay, discoloration,decoloration or formation of mould. In addition, the inventive compoundscan be used to protect objects which come into contact with saltwater orbrackish water, especially hulls, screens, nets, buildings, moorings andsignalling systems, from fouling.

The inventive method for controlling unwanted fungi can also be employedfor protecting storage goods. Storage goods are understood to meannatural substances of vegetable or animal origin or processed productsthereof which are of natural origin, and for which long-term protectionis desired. Storage goods of vegetable origin, for example plants orplant parts, such as stems, leaves, tubers, seeds, fruits, grains, canbe protected freshly harvested or after processing by (pre)drying,moistening, comminuting, grinding, pressing or roasting. Storage goodsalso include timber, both unprocessed, such as construction timber,electricity poles and barriers, or in the form of finished products,such as furniture. Storage goods of animal origin are, for example,hides, leather, furs and hairs. The inventive active ingredients mayprevent adverse effects, such as rotting, decay, discoloration,decoloration or formation of mould.

Non-limiting examples of pathogens of fungal diseases which can betreated in accordance with the invention include:

diseases caused by powdery mildew pathogens, for example Blumeriaspecies, for example Blumeria graminis; Podosphaera species, for examplePodosphaera leucotricha; Sphaerotheca species, for example Sphaerothecafuliginea; Uncinula species, for example Uncinula necator;diseases caused by rust disease pathogens, for example Gymnosporangiumspecies, for example Gymnosporangium sabinae; Hemileia species, forexample Hemileia vastatrix; Phakopsora species, for example Phakopsorapachyrhizi and Phakopsora meibomiae; Puccinia species, for examplePuccinia recondita or Puccinia triticina; Uromyces species, for exampleUromyces appendiculatus;diseases caused by pathogens from the group of the Oomycetes, forexample Bremia species, for example Bremia lactucae; Peronosporaspecies, for example Peronospora pisi or P. brassicae; Phytophthoraspecies, for example Phytophthora infestans; Plasmopara species, forexample Plasmopara viticola; Pseudoperonospora species, for examplePseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,for example Pythium ultimum;leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, for example Alternaria solani; Cercospora species,for example Cercospora beticola; Cladiosporium species, for exampleCladiosporium cucumerinum; Cochliobolus species, for exampleCochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium);Colletotrichum species, for example Colletotrichum lindemuthanium;Cycloconium species, for example Cycloconium oleaginum; Diaporthespecies, for example Diaporthe citri; Elsinoe species, for exampleElsinoe fawcettii; Gloeosporium species, for example Gloeosporiumlaeticolor; Glomerella species, for example Glomerella cingulate;Guignardia species, for example Guignardia bidwelli; Leptosphaeriaspecies, for example Leptosphaeria maculans; Magnaporthe species, forexample Magnaporthe grisea; Microdochium species, for exampleMicrodochium nivale; Mycosphaerella species, for example Mycosphaerellagraminicola and M. fijiensis; Phaeosphaeria species, for examplePhaeosphaeria nodorum; Pyrenophora species, for example Pyrenophorateres; Ramularia species, for example Ramularia collo-cygni;Rhynchosporium species, for example Rhynchosporium secalis; Septoriaspecies, for example Septoria apii; Typhula species, for example Typhulaincamata; Venturia species, for example Venturia inaequalis;root and stem diseases caused, for example, by Corticium species, forexample Corticium graminearum; Fusarium species, for example Fusariumoxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis;Rhizoctonia species, for example Rhizoctonia solani; Tapesia species,for example Tapesia acuformis; Thielaviopsis species, for exampleThielaviopsis basicola;ear and panicle diseases (including maize cobs) caused, for example, byAlternaria species, for example Alternaria spp.; Aspergillus species,for example Aspergillus flavus; Cladosporium species, for exampleCladosporium cladosporioides; Claviceps species, for example Clavicepspurpurea; Fusarium species, for example Fusarium culmorum; Gibberellaspecies, for example Gibberella zeae; Monographella species, for exampleMonographella nivalis; Septoria species, for example Septoria nodorum;diseases caused by smut fungi, for example Sphacelotheca species, forexample Sphacelotheca reiliana; Tilletia species, for example Tilletiacaries, T. controversa; Urocystis species, for example Urocystisocculta; Ustilago species, for example Ustilago nuda, U. nuda tritici;fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum;Verticilium species, for example Verticilium alboatrum;seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, for exampleFusarium culmorum; Phytophthora species, for example Phytophthoracactorum; Pythium species, for example Pythium ultimum; Rhizoctoniaspecies, for example Rhizoctonia solani; Sclerotium species, for exampleSclerotium rolfsii;cancers, galls and witches' broom caused, for example, by Nectriaspecies, for example Nectria galligena;wilt diseases caused, for example, by Monilinia species, for exampleMonilinia laxa;deformations of leaves, flowers and fruits caused, for example, byTaphrina species, for example Taphrina deformans;degenerative diseases of woody plants caused, for example, by Escaspecies, for example Phaeomoniella chlamydospora and Phaeoacremoniumaleophilum and Fomitiporia mediterranea;diseases of flowers and seeds caused, for example, by Botrytis species,for example Botrytis cinerea;diseases of plant tubers caused, for example, by Rhizoctonia species,for example Rhizoctonia solani; Helminthosporium species, for exampleHelminthosporium solani;diseases caused by bacterial pathogens, for example Xanthomonas species,for example Xanthomonas campestris pv. oryzae; Pseudomonas species, forexample Pseudomonas syringae pv. lachrymans; Erwinia species, forexample Erwinia amylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibutrispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglyeines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

Microorganisms capable of degrading or altering the industrial materialsinclude, for example, bacteria, fungi, yeasts, algae and slimeorganisms. The inventive active ingredients preferably act againstfungi, especially moulds, wood-discoloring and wood-destroying fungi(Basidiomycetes), and against slime organisms and algae. Examplesinclude microorganisms of the following genera: Alternaria, such asAlternaria tenuis; Aspergillus, such as Aspergillus niger, Chaetomium,such as Chaetomium globosum; Coniophora, such as Coniophora puetana;Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicilliumglaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such asAureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila;Trichoderma, such as Trichoderma viride; Escherichia, such asEscherichia coli; Pseudomonas, such as Pseudomonas aeruginosa;Staphylococcus, such as Staphylococcus aureus.

In addition, the inventive active ingredients also have very goodantimycotic activity. They have a very broad antimycotic activityspectrum, especially against dermatophytes and yeasts, moulds anddiphasic fungi (for example against Candida species, such as Candidaalbicans, Candida glabrata), and Epidermophyton floccosum, Aspergillusspecies, such as Aspergillus niger and Aspergillus fumigatus,Trichophyton species, such as Trichophyton mentagrophytes, Microsporonspecies such as Microsporon canis and audouinii. The list of these fungiby no means constitutes a restriction of the mycotic spectrum covered,and is merely of illustrative character.

The inventive active ingredients can therefore be used both in medicaland in non-medical applications.

When using the inventive active ingredients as fungicides, theapplication rates can be varied within a relatively wide range,depending on the kind of application. The application rate of theinventive active ingredients is

-   -   in the case of treatment of plant parts, for example leaves:        from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more        preferably from 50 to 300 g/ha (in the case of application by        watering or dripping, it is even possible to reduce the        application rate, especially when inert substrates such as        rockwool or perlite are used);    -   in the case of seed treatment: from 2 to 200 g per 100 kg of        seed, preferably from 3 to 150 g per 100 kg of seed, more        preferably from 2.5 to 25 g per 100 kg of seed, even more        preferably from 2.5 to 12.5 g per 100 kg of seed;    -   in the case of soil treatment: from 0.1 to 10 000 g/ha,        preferably from 1 to 5000 g/ha.        These application rates are merely by way of example and are not        limiting for the purposes of the invention.

The inventive active ingredients or compositions can thus be used toprotect plants from attack by the pathogens mentioned for a certainperiod of time after treatment. The period for which protection isprovided extends generally for 1 to 28 days, preferably for 1 to 14days, more preferably for 1 to 10 days, most preferably for 1 to 7 days,after the treatment of the plants with the active ingredients, or for upto 200 days after a seed treatment In addition, the inventive treatmentcan reduce the mycotoxin content in the harvested material and the foodsand feeds prepared therefrom. Mycotoxins include particularly, but notexclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON,3-Ac-DON, T2- and HT2-toxin, fumonisins, zearalenon, moniliformin,fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin,fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids andaflatoxins which can be produced, for example, by the following fungi:Fusarium spec., such as Fusarium acuminatum, F. avenaceum, F.crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F.equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F.poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F.solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F.tricinctum, F. verticillioides, inter alia, and also by Aspergillusspec., Penicillium spec., Claviceps purpurea, Stachybotrys spec., interalia.

In some cases, the inventive compounds can, at particular concentrationsor application rates, also be used as herbicides, safeners, growthregulators or agents to improve plant properties, or as microbicides,for example as fungicides, antimycotics, bactericides, viricides(including compositions against viroids) or as compositions against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be used as intermediates or precursors forthe synthesis of other active ingredients.

The inventive active ingredients intervene in the metabolism of theplants and can therefore also be used as growth regulators.

Plant growth regulators may exert various effects on plants. The effectof the substances depends essentially on the time of application inrelation to the developmental stage of the plant, and also on theamounts of active ingredient applied to the plants or their environmentand on the type of application. In each case, growth regulators shouldhave a particular desired effect on the crop plants.

Plant growth-regulating compounds can be used, for example, to inhibitthe vegetative growth of the plants. Such inhibition of growth is ofeconomic interest, for example, in the case of grasses, since it is thuspossible to reduce the frequency of grass cutting in ornamental gardens,parks and sport facilities, on roadsides, at airports or in fruit crops.Also of significance is the inhibition of the growth of herbaceous andwoody plants on roadsides and in the vicinity of pipelines or overheadcables, or quite generally in areas where vigorous plant growth isunwanted.

Also important is the use of growth regulators for inhibition of thelongitudinal growth of cereal. This reduces or completely eliminates therisk of lodging of the plants prior to harvest. In addition, growthregulators in the case of cereals can strengthen the culm, which alsocounteracts lodging. The employment of growth regulators for shorteningand strengthening culms allows the deployment of higher fertilizervolumes to increase the yield, without any risk of lodging of the cerealcrop.

In many crop plants, inhibition of vegetative growth allows denserplanting, and it is thus possible to achieve higher yields based on thesoil surface. Another advantage of the smaller plants obtained in thisway is that the crop is easier to cultivate and harvest.

Inhibition of the vegetative plant growth may also lead to enhancedyields because the nutrients and assimilates are of more benefit toflower and fruit formation than to the vegetative parts of the plants.

Frequently, growth regulators can also be used to promote vegetativegrowth. This is of great benefit when harvesting the vegetative plantparts. However, promoting vegetative growth may also promote generativegrowth in that more assimilates are formed, resulting in more or largerfruits.

In some cases, yield increases may be achieved by manipulating themetabolism of the plant, without any detectable changes in vegetativegrowth. In addition, growth regulators can be used to alter thecomposition of the plants, which in turn may result in an improvement inquality of the harvested products. For example, it is possible toincrease the sugar content in sugar beet, sugar cane, pineapples and incitrus fruit, or to increase the protein content in soya or cereals. Itis also possible, for example, to use growth regulators to inhibit thedegradation of desirable ingredients, for example sugar in sugar beet orsugar cane, before or after harvest. It is also possible to positivelyinfluence the production or the elimination of secondary plantingredients. One example is the stimulation of the flow of latex inrubber trees.

Under the influence of growth regulators, parthenocarpic fruits may beformed. In addition, it is possible to influence the sex of the flowers.It is also possible to produce sterile pollen, which is of greatimportance in the breeding and production of hybrid seed.

Use of growth regulators can control the branching of the plants. On theone hand, by breaking apical dominance, it is possible to promote thedevelopment of side shoots, which may be highly desirable particularlyin the cultivation of ornamental plants, also in combination with aninhibition of growth. On the other hand, however, it is also possible toinhibit the growth of the side shoots. This effect is of particularinterest, for example, in the cultivation of tobacco or in thecultivation of tomatoes.

Under the influence of growth regulators, the amount of leaves on theplants can be controlled such that defoliation of the plants is achievedat a desired time. Such defoliation plays a major role in the mechanicalharvesting of cotton, but is also of interest for facilitatingharvesting in other crops, for example in viticulture. Defoliation ofthe plants can also be undertaken to lower the transpiration of theplants before they are transplanted.

Growth regulators can likewise be used to regulate fruit dehiscence. Onthe one hand, it is possible to prevent premature fruit dehiscence. Onthe other hand, it is also possible to promote fruit dehiscence or evenflower abortion to achieve a desired mass (“thinning”), in order toeliminate alternation. Alternation is understood to mean thecharacteristic of some fruit species, for endogenous reasons, to deliververy different yields from year to year. Finally, it is possible to usegrowth regulators at the time of harvest to reduce the forces requiredto detach the fruits, in order to allow mechanical harvesting or tofacilitate manual harvesting.

Growth regulators can also be used to achieve faster or else delayedripening of the harvested material before or after harvest. This isparticularly advantageous as it allows optimal adjustment to therequirements of the market. Moreover, growth regulators in some casescan improve the fruit colour. In addition, growth regulators can also beused to concentrate maturation within a certain period of time. Thisestablishes the prerequisites for complete mechanical or manualharvesting in a single operation, for example in the case of tobacco,tomatoes or coffee.

By using growth regulators, it is additionally possible to influence theresting of seed or buds of the plants, such that plants such aspineapple or ornamental plants in nurseries, for example, germinate,sprout or flower at a time when they are normally not inclined to do so.In areas where there is a risk of frost, it may be desirable to delaybudding or germination of seeds with the aid of growth regulators, inorder to avoid damage resulting from late frosts.

Finally, growth regulators can induce resistance of the plants to frost,drought or high salinity of the soil. This alto lows the cultivation ofplants in regions which are normally unsuitable for this purpose.

The plants listed can particularly advantageously be treated inaccordance with the invention with the compounds of the general formula(I) and the inventive compositions. The preferred ranges stated abovefor the active ingredients or compositions also apply to the treatmentof these plants. Particular emphasis is given to the treatment of plantswith the compounds or compositions specifically mentioned in the presenttext.

The invention is illustrated by the examples below. However, theinvention is not limited to the examples.

PREPARATION EXAMPLES Preparation of Compound No. 2 (Process C)

To 0.52 g (3.0 mmol) of 4-bromophenol dissolved in 10 ml ofN,N-dimethylformamide was added, at room temperature under an argonatmosphere, 0.12 g (60%, 3.0 mmol) of sodium hydride, and the reactionmixture was stirred at room temperature for 1 h. Then 0.50 g (2.7 mmol)of 5-(2-tert-butyloxiran-2-yl)-1,3-thiazole was added and the reactionmixture was stirred at 100° C. for 12 h. After cooling to roomtemperature, the solvent was removed under reduced pressure, andsaturated aqueous sodium chloride solution and ethyl acetate were addedto the residue. The organic phase was removed, dried over sodiumsulphate, filtered and concentrated. The crude product was then purifiedby column chromatography (3:1 cyclohexane/ethyl acetate). This gave 0.12g (13%) of the desired product.

Preparation of 5-(2-tert-butyloxiran-2-yl)-1,3-thiazole

The preparation is effected analogously to the process described in EP-A0 409 418.

Preparation of Compound No. 4 (Process C)

To 0.55 g (2.5 mmol) of 4-iodophenol dissolved in 10 ml ofN,N-dimethylformamide was added, at room temperature under an argonatmosphere, 0.1 g (60%, 2.5 mmol) of sodium hydride, and the reactionmixture was stirred at room temperature for 1 h. Then 0.50 g (2.3 mmol)of 5-[2-(1,3-difluoro-2-methylpropan-2-yl)oxiran-2-yl]-1,3-thiazole wasadded and the reaction mixture was stirred at 100° C. for 12 h. Aftercooling to room temperature, the solvent was removed under reducedpressure, and saturated aqueous sodium chloride solution and ethylacetate were added to the residue. The organic phase was removed, driedover sodium sulphate, filtered and concentrated. The crude product wasthen purified by column chromatography (5:1 cyclohexane/ethyl acetate).This gave 0.17 g (17%) of the desired product.

5-[2-(1,3-Difluoro-2-methylpropan-2-yl)oxiran-2-yl]-1,3-thiazole

To 2.00 g (12.7 mmol) of 2-trimethylsilyl-1,3-thiazole dissolved in 20ml of diethyl ether were added, at −78° C. under an argon atmosphere,5.1 ml (2.5 M, 12.7 mmol) of n-butyllithium, and the reaction mixturewas stirred at −78° C. for 20 min. Then 2.73 g (12.7 mmol) of1-bromo-4-fluoro-3-(fluoromethyl)-3-methylbutan-2-one were added and thereaction mixture was gradually warmed to room temperature. Afteraddition of saturated aqueous ammonium chloride solution, the phaseswere separated and the aqueous phase was extracted with diethyl ether.The combined organic phases were dried over sodium sulphate, filteredand concentrated. The crude product was then purified by columnchromatography (5:1 cyclohexane/ethyl acetate). This gave 2.39 g (86%)of the desired product.

Preparation of Compound No. 5 (Process B)

To 300 mg (1.90 mmol) of 2-trimethylsilyl-1,3-thiazole dissolved in 2 mlof diethyl ether were added, at −78° C. under an argon atmosphere, 1.3ml (1.5 M, 1.95 mmol) of n-butyllithium, and the reaction mixture wasstirred at −78° C. for 30 min. Then 429 mg (1.9 mmol) of1-(4-chlorophenyl)-4,4-dimethylpentan-3-one in 2 ml of diethyl etherwere added and the reaction mixture was gradually warmed to roomtemperature. After addition of saturated aqueous ammonium chloridesolution, the phases were separated and the aqueous phase was extractedwith diethyl ether. The combined organic phases were dried over sodiumsulphate, filtered and concentrated. The crude product was then purifiedby column chromatography (3:1 hexane/ethyl acetate). This gave 154 mg(26%) of the desired product.

Preparation of Compound No. 7 (Process B)

To 300 mg (1.90 mmol) of 2-trimethylsilyl-1,3-thiazole dissolved in 2 mlof diethyl ether were added, at −78° C. under an argon atmosphere, 1.3ml (1.5 M, 1.95 mmol) of n-butyllithium, and the reaction mixture wasstirred at −78° C. for 30 min. Then 437 mg (1.90 mmol) of1-(1-chlorocyclopropyl)-2-(2-chlorophenyl)ethanone in 2 ml of diethylether were added and the reaction mixture was gradually warmed to roomtemperature. After addition of saturated aqueous ammonium chloridesolution, the phases were separated and the aqueous phase was extractedwith diethyl ether. The combined organic phases were dried over sodiumsulphate, filtered and concentrated. The crude product was then purifiedby column chromatography (3:1 cyclohexane/ethyl acetate). This gave 433mg (72%) of the desired product.

Preparation of Compound No. 13 (Process D)

To 1.00 g (8.4 mmol) of 2-chloro-1,3-thiazole dissolved in 25 ml oftetrahydrofuran were added, at −78° C. under an argon atmosphere, 3.2 ml(2.5 M, 8.0 mmol) of n-butyllithium, and the reaction mixture wasstirred at −78° C. for 10 min. Then 1.816 g (7.6 mmol) of2-tert-butyl-4-(4-chlorophenyl)-1,2-epoxybutane were added and thereaction mixture was gradually warmed to room temperature. Afteraddition of water, the phases were separated and the aqueous phase wasextracted with ethyl acetate. The combined organic phases were driedover magnesium sulphate, filtered and concentrated. The crude productwas then purified by column chromatography with cyclohexane/ethylacetate (gradient). This gave 0.65 g (24%) of the desired product.

Preparation of Compound No. 18 (Process F)

404 mg (1.13 mmol) of compound 17, prepared by the synthesis methoddescribed above, were dissolved in 15 ml of acetic acid, and 222 mg(3.39 mmol) of zinc dust were added. Then the reaction mixture washeated to reflux and refluxed for 2 h. Addition of aqueous ammonia wasfollowed by extraction with ethyl acetate. The combined organic phaseswere dried over magnesium sulphate, filtered and concentrated. This gave0.360 g (98%) of the desired product.

Preparation of Compound No. 12 (Process E)

To 0.3 g (1.0 mmol) of1-(4-chlorophenoxy)-3,3-dimethyl-2-(1,3-thiazol-5-yl)butan-2-oldissolved in 12 ml of tetrahydrofuran was added, at −78° C. under anargon atmosphere, 0.85 ml (2.5 M, 2.1 mmol) of n-butyllithium, and thereaction mixture was stirred at −78° C. for 1 h. Then 0.15 g (4.8 mmol)of sulphur powder was added and the reaction mixture was warmed to roomtemperature. After stirring at this temperature for 3 h, water was addedand the reaction mixture was extracted with ethyl acetate. The combinedorganic phases were dried over sodium sulphate, filtered andconcentrated. The crude product was then purified by columnchromatography (1:1 cyclohexane/ethyl acetate). This gave 0.08 g (25%)of the desired product.

Preparation of compound No. 48 (process A)

To 0.20 g (1.2 mmol) of 2,2-dimethyl-1-(1,3-thiazol-5-yl)propan-1-onedissolved in 5 ml of diethyl ether were added, at −10° C. under an argonatmosphere, 14 ml (0.25 M in diethyl ether, 3.5 mmol) of4-fluorobenzylmagnesium bromide, and the reaction mixture was warmed toroom temperature. The reaction mixture was then stirred at roomtemperature for 12 h. After addition of saturated aqueous ammoniumchloride solution, the phases were separated and the aqueous phase wasextracted with ethyl acetate. The combined organic phases were driedover sodium sulphate, filtered and concentrated. The crude product wasthen purified by column chromatography (5:1 cyclohexane/ethyl acetate).This gave 0.11 g (33%) of the desired product.

TABLE 1 (I)

No. X Y m n R R¹ A Physical data 1 S O 0 0 tBu H 4-iodophenyl ¹H NMR: δ(400 MHz, DMSO-d6) = 0.97 (s, 9H), 4.15 (d, J = 10 Hz, 1H), 4.37 (d, J =10 Hz, 1H), 5.72 (s, 1H), 6.79-6.81 (m, 2H), 7.55-7.58 (m, 2H), 7.74 (s,1H), 8.92 (s, 1H) ppm 2 S O 0 0 tBu H 4-bromophenyl ¹H NMR: δ (400 MHz,DMSO-d6) = 0.98 (s, 9H), 4.16 (d, J = 10 Hz, 1H), 4.38 (d, J = 10 Hz,1H), 5.71 (s, 1H), 6.91-6.93 (m, 2H), 7.41-7.43 (m, 2H), 7.74 (s, 1H),8.92 (s, 1H) ppm 3 S O 0 0 tBu H 4-[(E)- ¹H NMR: δ (400 MHz, DMSO-d6) =0.99 (s, (methoxy- 9H), 3.85 (s, 3H), 4.20 (d, J = 10 Hz, 1H), 4.42imino)methyl]phenyl (d, J = 10 Hz, 1H), 5.74 (s, 1H), 6.97-6.99 (m, 2H),7.51-7.53 (m, 2H), 7.75 (s, 1H), 8.13 (s, 1H), 8.92 (s, 1H) ppm 4 S O 00 DFMP H 4-iodophenyl logP 3.16^([a]); [M + H]⁺ = 440. 5 S CH₂ 0 0 tBu H4-chlorophenyl ¹H NMR: δ (400 MHz, CD₃CN) = 0.94 (s, 9H), 2.13-2.24 (m,3H), 2.58-2.69 (m, 1H), 3.38 (s, 1H), 7.14 (d, 2H), 7.26 (d, 2H), 7.69(s, 1H), 8.75 (s, 1H), ppm 6 S CH₂ 0 0 tBu H 4- ¹H NMR: δ (400 MHz,CD₃CN) = 0.95 (s, 9H), [(trifluorometh- 2.17-2.25 (m, 3H), 2.68-2.72 (m,1H), 3.44 (s, yl)sulphanyl]phenyl 1H), 7.29 (d, 2H), 7.59 (d, 2H), 7.70(s, 1H), 8.76 (s, 1H), ppm 7 S — 0 0 CCP H 2-chlorophenyl ¹H NMR: δ (400MHz, DMSO-d6) = 0.82-0.91 (m, 1H), 0.93-1.00 (m, 1H), 1.12-1.18 (m, 1H),1.28-1.35 (m, 1H), 3.52 (d, 1H), 3.72 (d, 1H), 6.03 (s, 1H), 7.18-7.23(m, 2H), 7.33-7.37 (m, 1H), 7.52-7.56 (m, 1H), 7.82 (s, 1H), 8.95 (s,1H) ppm 8 S O 0 0 DFMP H 4-bromophenyl logP 3.02^([a]); [M + H]⁺ =392/394. 9 S O 0 0 DFMP H 4-chlorophenyl logP 2.94^([a]); [M + H]⁺ = 34810 S — 0 0 CCP H 2-fluorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.77-0.85(m, 2H), 0.90-0.93 (m, 1H), 1.24-1.28 (m, 1H), 3.43 (d, J = 14 Hz, 1H),3.54 (d, J = 14 Hz, 1H), 6.17 (s, 1H), 7.07-7.10 (m, 2H), 7.24-7.28 (m,1H), 7.45-7.48 (m, 1H), 7.91 (s, 1H), 8.99 (s, 1H) ppm 11 S — 0 0 FCP H2-chlorophenyl logP 2.64^([a]); [M + H]⁺ = 298 12 S O 0 0 tBu SH4-chlorophenyl logP 3.06^([a]); [M + H]⁺ = 344 13 S CH₂ 0 1 tBu Cl4-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.96 (s, 9H), 1.61 (m,1H), 1.73 (m, 1H), 2.30-2.55 (m, 2H), 2.95 (d, J = 15 Hz, 1H), 3.18 (d,J = 15 Hz, 1H), 4.64 (s, 1H, OH), 7.06 (d, 2H), 7.27 (d, 2H), 7.56 (s,1H), ppm 14 S O 0 0 MCP H 4-chlorophenyl logP 3.11^([a]); [M + H]⁺ =310; 312 15 S O 0 0 tBu H 2-fluorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) =0.99 (s, 9H), 4.24 (d, J = 10 Hz, 1H), 4.41 (d, J = 10 Hz, 1H), 5.74 (s,1H), 6.94-6.95 (m, 1H), 7.12-7.22 (m, 3H), 7.79 (s, 1H), 8.93 (s, 1H)ppm 16 S O 0 0 CCP H 4-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) =0.85-0.95 (m, 1H), 1.08-1.20 (m, 1H), 1.28-1.40 (m, 1H), 1.50-1.62 (m,1H), 4.49 (q, 2H), 6.39 (s, 1H), 7.08 (d, 2H), 7.35 (d, 2H), 7.99 (s,1H), 9.04 (s, 1H) ppm 17 S O 0 0 iPr H 4- ¹H NMR: δ (400 MHz, DMSO-d6) =0.81 (d, [(trifluorometh- 3H), 0.90 (d, 3H), 2.28 (septet, 1H), 4.15 (d,1H), yl)sulphanyl]phenyl 4.23 (d, 1H), 5.81 (s, 1H), 7.09-7.13 (m, 2H),7.62 (d, 2H), 7.80 (s, 1H), 8.95 (s, 1H) ppm 18 S CH₂ 0 1 tBu H4-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.96 (s, 9H), 1.60 (m,1H), 1.71 (m, 1H), 2.27-2.56 (m, 2H), 2.98 (d, J = 15 Hz, 1H), 3.22 (d,J = 15 Hz, 1H), 4.38 (s, 1H, OH), 7.03 (d, 2H), 7.26 (d, 2H), 7.77 (s,1H) ppm, 8.91 (s, 1H) ppm 19 S O 0 0 tBu H 4′-iodobiphenyl-4-yl logP4.89^([a]); [M + H]⁺ = 480 20 S O 0 0 tBu H 4- ¹H NMR: δ (400 MHz,DMSO-d6) = 0.98 (s, (trifluoromethoxy)phenyl 9H), 4.18 (d, J = 10 Hz,1H), 4.42 (d, J = 10 Hz, 1H), 5.74 (s, 1H), 7.03-7.05 (m, 1H), 7.25-7.27(m, 2H), 7.76 (s, 1H), 8.93 (s, 1H) ppm 21 S O 0 0 iPr H 4-iodophenyl ¹HNMR: δ (400 MHz, DMSO-d6) = 0.80 (d, 3H), 0.89 (d, 3H), 2.25 (septet,1H), 4.05 (d, 1H), 4.13 (d, 1H), 5.76 (s, 1H), 6.78-6.84 (m, 2H),7.55-7.60 (m, 2H), 7.78 (s, 1H), 8.94 (s, 1H) ppm 22 S O 0 0 iPr H4-bromophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.80 (d, 3H), 0.89 (d, 3H),2.26 (septet, 1H), 4.07 (d, 1H), 4.15 (d, 1H), 5.77 (s, 1H), 6.92-6.97(m, 2H), 7.42-7.47 (m, 2H), 7.78 (s, 1H), 8.94 (s, 1H) ppm 23 S O 0 0iPr H 4-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.80 (d, 3H), 0.90(d, 3H), 2.26 (septet, 1H), 4.07 (d, 1H), 4.15 (d, 1H), 5.76 (s, 1H),6.96-6.71 (m, 2H), 7.29-7.34 (m, 2H), 7.78 (s, 1H), 8.94 (s, 1H) ppm 24S O 0 0 MCP H 2-bromophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.12-0.18 (m,1H), 0.35-0.42 (m, 1H), 0.88-0.93 (m, 1H), 1.01 (s, 3H), 1.08-1.16 (m,1H), 4.37 (s, 2H), 5.68 (s, 1H), 6.91 (td, 1H), 7.22 (dd, 1H), 7.35 (td,1H), 7.58 (dd, 1H), 7.96 (s, 1H), 8.98 (s, 1H) ppm 25 S O 0 0 MCH H4-iodophenyl logP 4.53^([a]); [M + H]⁺ = 444 26 S O 0 0 MCP H3-iodophenyl logP 3.41^([a]); [M + H]⁺ = 402 27 S O 0 0 MCP H3-bromophenyl logP 3.24^([a]); [M + H]⁺ = 354, 356 28 S O 0 0 tBu H4-(4- logP 4.66^([a]); [M + H]⁺ = 448/450 bromophenoxy)phenyl 29 S O 0 0tBu H 4-(4- logP 4.50^([a]); [M + H]⁺ = 404 chlorophenoxy)phenyl 30 S O0 0 tBu H 4′-(trifluoromethyl)- logP 4.62^([a]); [M + H]⁺ = 422biphenyl-4-yl 31 S O 0 0 tBu H 4′-acetylbiphenyl- ¹H NMR: δ (400 MHz,DMSO-d6) = 1.00 (s, 4-yl 9H), 2.59 (s, 3H), 4.24 (d, J = 10 Hz, 1H),4.46 (d, J = 10 Hz, 1H), 5.75 (s, 1H), 7.06-7.08 (m, 2H), 7.67-7.70 (m,2H), 7.76-7.78 (m, 3H), 7.99- 8.01 (m, 2H), 8.94 (s, 1H) ppm 32 S O 0 0tBu H 4-[4- logP 4.63^([a]); [M + H]⁺ = 438 (trifluorometh-yl)phenoxy]phenyl 33 S O 0 0 MCH H 4-bromophenyl logP 4.37^([a]); [M +H]⁺ = 396/398 34 S O 0 0 MCH H 4-chlorophenyl logP 4.25^([a]); [M + H]⁺= 352 35 S O 0 0 tBu H 4′-methoxybiphenyl-4-yl ¹H NMR: δ (400 MHz,DMSO-d6) = 1.00 (s, 9H), 3.77 (s, 3H), 4.20 (d, J = 10 Hz, 1H), 4.42 (d,J = 10 Hz, 1H), 5.72 (s, 1H), 6.97-7.01 (m, 4H), 7.49-7.54 (m, 4H), 7.77(s, 1H), 8.93 (s, 1H) ppm 36 S O 0 0 tBu H 4′-chlorobiphenyl-4-yl logP4.55^([a]); [M + H]⁺ = 388 37 S O 0 0 tBu H 4-cyclohexylphenyl logP5.21^([a]); [M + H]⁺ = 360 38 S O 0 0 tBu H 4-(4- logP 4.03^([a]); [M +H]⁺ = 388 fluorophenoxy)phenyl 39 S — 0 1 CCP I 2-chlorophenyl ¹H NMR: δ(400 MHz, DMSO-d6) = 0.55-0.59 (m, 1H), 0.68-0.73 (m, 1H), 0.81-0.87 (m,1H), 0.92-0.96 (m, 1H), 2.85 (d, 1H), 2.99 (d, 1H), 3.48 (d, 1H), 3.51(d, 1H), 5.14 (s, 1H, OH), 7.25-7.28 (m, 2H), 7.39 (s, 1H), 7.39-7.41(dd, 1H), 7.54-7.56 (dd, 1H) ppm 40 S O 0 0 tBu H 4-tert-butylphenyllogP 4.39^([a]); [M + H]⁺ = 334 41 S O 0 0 tBu H 4- logP 3.98^([a]);[M + H]⁺ = 378 [(trifluorometh- yl)sulphanyl]phenyl 42 S O 0 0 tBu H4-fluorophenyl logP 2.91^([a]); [M + H]⁺ = 296 43 S O 0 0 tBu H3-phenoxyphenyl logP 3.98^([a]); [M + H]⁺ = 370 44 S O 0 0 tBu H4-phenoxyphenyl logP 3.96^([a]); [M + H]⁺ = 388 45 S O 0 0 MCP H3-nitrophenyl logP 2.62^([a]); [M + H]⁺ = 321 46 S — 0 0 DFMP H2-chlorophenyl logP 2.78^([a]); [M + H]⁺ = 332 47 S — 0 0 DFMP H2-fluorophenyl logP 2.47^([a]); [M + H]⁺ = 316 48 S — 0 0 tBu H4-fluorophenyl logP 2.91^([a]); [M + H]⁺ = 280 49 S O 0 0 tBu H3-methoxybiphenyl-4-yl logP 4.02^([a]); [M + H]⁺ = 384 50 S O 0 0 tBu Hbiphenyl-4-yl logP 4.03^([a]); [M + H]⁺ = 354 51 S O 0 0 tBu H4′-cyanobiphenyl-4-yl logP 3.46^([a]); [M + H]⁺ = 379 52 S O 0 0 tBu H4′-bromobiphenyl-4-yl logP 4.71^([a]); [M + H]⁺ = 432/434 53 S O 0 0 CMBH 4-iodophenyl logP 3.92^([a]); [M + H]⁺ = 450 54 S O 0 0 CMB H4-chlorophenyl logP 3.67^([a]); [M + H]⁺ = 358 55 S O 0 0 MCP H2-iodophenyl logP 3.33^([a]); [M + H]⁺ = 402 56 S — 0 1 CCP Cl2-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.59-0.63 (m, 1H),0.70-0.75 (m, 1H), 0.89-1.00 (m, 2H), 2.82 (d, 1H), 3.00 (d, 1H), 3.44(d, 1H), 3.53 (d, 1H), 5.23 (s, 1H, OH), 7.24-7.30 (m, 2H), 7.39- 7.41(dd, 1H), 7.44 (s, 1H), 7.54-7.56 (dd, 1H) ppm 57 S — 0 1 CCP H2-chlorophenyl ¹H NMR: δ (400 MHz, DMSO-d6) = 0.47-0.52 (m, 1H),0.64-0.70 (m, 1H), 0.73-0.80 (m, 1H), 0.89-0.94 (m, 1H), 2.85 (d, 1H),3.02 (d, 1H), 3.49 (d, 1H), 3.53 (d, 1H), 5.03 (s, 1H, OH), 7.24-7.31(m, 2H), 7.40-7.43 (dd, 1H), 7.56-7.59 (dd, 1H), 7.68 (s, 1H), 8.90 (s,1H) ppm 58 S O 0 0 tBu H 4- logP 4.23^([a]); [M + H]⁺ = 394{[chloro(difluoro)methyl]- sulphanyl}phenyl 59 S — 0 1 CCP Cl2-fluorophenyl logP 4.21^([a]); [M + H]⁺ = 346 60 S — 0 1 CCP H2-fluorophenyl logP 3.06^([a]); [M + H]⁺ = 312 61 S O 0 1 tBu Cl4-chlorophenyl logP 4.68^([a]); [M + H]⁺ = 360 62 S O 0 1 tBu Cl4-iodophenyl logP 5.12^([a]); [M + H]⁺ = 452 63 S O 0 1 tBu Cl4-fluorophenyl logP 4.20^([a]); [M + H]⁺ = 344 64 S O 0 1 tBu H4-chlorophenyl logP 3.49^([a]); [M + H]⁺ = 326 65 S O 0 1 DFMP Cl4-chlorophenyl logP 3.94^([a]); [M + H]⁺ = 397 66 S O 0 1 tBu H4-fluorophenyl logP 3.16^([a]); [M + H]⁺ = 310 67 S O 0 1 DFMP H4-chlorophenyl logP 3.04^([a]); [M + H]⁺ = 362 68 O — 0 0 CCP iPr₃Si2-chlorophenyl logP 7.18^([a]); [M + H]⁺ = 455 69 O — 0 0 CCP H2-chlorophenyl logP 2.88^([a]); [M + H]⁺ = 299 70 O CH₂ 0 0 tBu iPr₃Si4-chlorophenyl logP 7.36^([a]); [M + H]⁺ = 451 71 O CH₂ 0 0 tBu H4-chlorophenyl logP 3.45^([a]); [M + H]⁺ = 294 72 S CH₂ 0 0 tBu H4-bromophenyl logP 3.69^([a]); [M + H]⁺ = 354, 356 73 S CH₂ 0 0 tBu H4-methoxyphenyl logP 2.94^([a]); [M + H]⁺ = 306 74 S CH₂ 0 0 tBu H 4-logP 3.93^([a]); [M + H]⁺ = 360 (trifluoromethoxy)phenyl 75 S CH₂ 0 0tBu H 4-nitrophenyl logP 2.98^([a]); [M + H]⁺ = 321 76 S CH₂ 0 0 tBu H4-aminophenyl logP 1.16; [M + H]⁺ = 291 77 S CH₂ 0 0 tBu H4-tert-butylphenyl logP 1.98^([a]); [M + H]⁺ = 333 78 S CH₂ 0 0 tBu H4-({(E)- logP 1.33^([a]); [M + H]⁺ = 360 [ethyl(methyl)amino]-methylene}amino)phenyl 79 S O 0 0 tBu H 4-cyclopropylphenyl logP3.73^([a]); [M + H]⁺ = 318 80 S O 0 0 tBu H 4-cyclopentylphenyl logP4.78^([a]); [M + H]⁺ = 346 81 S O 0 0 CF₃CP H 4-iodophenyl logP3.59^([a]); [M + H]⁺ = 456 82 S O 0 0 CF₃CP H 4-bromophenyl logP3.43^([a]); [M + H]⁺ = 408/410

-   -   iPr=isopropyl, tBu=tert-butyl,        DFMP=1,3-difluoro-2-methylpropan-2-yl, CCP=1-chlorocyclopropyl,        FCP=1-fluorocyclopropyl, MCP=1-methylcyclopropyl,        MCH=1-methylcyclohexyl, CMB=(3E)-4-chloro-2-methylbut-3-en-2-yl,        iPr₃Si=triisopropylsilyl, CF₃CP=1-(trifluoromethyl)cyclopropyl.

The logP values were measured in accordance with EEC Directive 79/831Annex V.A8 by HPLC (High Performance Liquid Chromatography) usingreversed-phase columns (C18) by the following methods:

[α] The LC-MS determination in the acidic range is effected at pH 2.7with 0.1% aqueous formic acid and acetonitrile (contains 0.1% formicacid) as eluents; linear gradient from 10% acetonitrile to 95%acetonitrile.[b] The LC-MS determination in the acidic range is effected at pH 2.3with 0.1% aqueous phosphoric acid and acetonitrile (contains 0.1%phosphoric acid) as eluents; linear gradient from 10% acetonitrile to95% acetonitrile.

NMR Data of Selected Examples in the Form of ¹H NMR Peak Lists

The ¹H NMR data of the selected examples which follow are noted in theform of ¹H NMR peak lists. For each signal peak, first the δ value inppm and then the signal intensity in brackets are listed, separated by aspace. The δ-signal intensity value pairs of different signal peaks arelisted separated from one another by semicolons. The peak list of oneexample therefore takes the form of

δ₁(intensity₁); δ₂(intensity₂); . . . . ; δ_(i)(intensity_(i)); . . . ;δ_(n) (intensity_(n))

The solvent in which the NMR spectrum was recorded is listed in squarebrackets after the Example number and before the NMR peak list. Adetailed description of the presentation of NMR data in the form of peaklists can be found in the publication “Citation of NMR Peaklist Datawithin Patent Applications” (cf. Research Disclosure Database Number564025, 2011, 16 March 2011 orhttp://www.rdelectronic.co.uk/rd/free/RD564025.pdf).

Example No. 58 [DMSO—D₆] 8.9329 (1.67); 7.7607 (1.82); 7.6114 (1.60);7.5895 (1.71); 7.1063 (1.89); 7.0841 (1.76); 5.8081 (1.28); 4.5053(0.76); 4.4808 (0.97); 4.2600 (0.85); 4.2352 (0.79); 3.3648 (183.72);3.3535 (157.51); 3.3487 (183.55); 3.3406 (255.13); 2.6766 (0.41); 2.6715(0.54); 2.5418 (1.01); 2.5066 (67.78); 2.5026 (89.89); 2.4986 (64.09);2.3292 (0.57); 1.1930 (0.94); 1.1730 (1.42); 1.1551 (0.33); 0.9836(16.00); 0.9542 (0.47); 0.9217 (0.38); 0.0080 (0.46); −0.0002 (16.40);−0.0084 (0.63) Example No. 59 [DMSO—D₆] 7.7272 (2.33); 7.6114 (0.33);7.5926 (0.53); 7.5725 (0.36); 7.5026 (0.48); 7.4649 (15.60); 7.4505(4.61); 7.4468 (4.79); 7.4320 (2.55); 7.4277 (2.42); 7.3062 (1.21);7.3018 (1.24); 7.2925 (1.72); 7.2871 (3.29); 7.2729 (2.77); 7.2682(3.47); 7.2630 (1.98); 7.2540 (1.96); 7.2496 (1.63); 7.1416 (7.17);7.1317 (2.50); 7.1229 (7.49); 7.1152 (5.17); 7.1072 (3.52); 7.1043(3.03); 7.0944 (2.84); 6.3923 (1.90); 5.3830 (0.49); 5.2197 (16.00);4.0810 (0.53); 4.0632 (0.57); 3.4644 (0.34); 3.4255 (0.59); 3.3994(5.53); 3.3619 (7.11); 3.3051 (799.84); 3.2359 (0.69); 3.2075 (4.55);3.1731 (5.89); 2.9872 (5.26); 2.9489 (7.44); 2.9100 (4.90); 2.6953(0.37); 2.6740 (0.98); 2.6694 (1.29); 2.6649 (0.99); 2.5616 (0.71);2.5395 (2.88); 2.5091 (77.91); 2.5049 (141.19); 2.5004 (181.14); 2.4961(126.96); 2.4918 (62.04); 2.3316 (0.97); 2.3271 (1.27); 2.3228 (0.93);2.0695 (1.26); 1.9868 (0.49); 1.3984 (10.91); 1.3584 (0.59); 1.3404(0.53); 1.2378 (0.48); 1.2224 (2.37); 1.2044 (2.27); 1.1104 (0.34);1.0922 (0.32); 0.8715 (1.25); 0.8619 (1.42); 0.8566 (1.70); 0.8468(3.18); 0.8353 (3.35); 0.8302 (3.59); 0.8201 (4.22); 0.8163 (3.90);0.8042 (3.65); 0.8009 (3.79); 0.7880 (3.30); 0.7780 (1.50); 0.7744(1.45); 0.7630 (1.50); 0.7357 (0.36); 0.7228 (0.38); 0.7134 (0.35);0.6427 (1.49); 0.6306 (1.78); 0.6276 (1.84); 0.6174 (3.69); 0.6042(3.34); 0.6013 (3.36); 0.5897 (2.87); 0.5684 (3.16); 0.5584 (3.38);0.5532 (3.21); 0.5416 (3.39); 0.5321 (1.96); 0.5269 (1.56); 0.5168(1.19); 0.4475 (0.33); 0.4430 (0.34); 0.4293 (0.32); −0.0002 (7.34)Example No. 60 [DMSO—D₆] 9.0426 (0.52); 8.9300 (0.59); 8.9116 (11.67);7.9477 (0.59); 7.7579 (0.41); 7.7269 (0.92); 7.7016 (11.49); 7.4836(2.44); 7.4679 (4.14); 7.4643 (4.63); 7.4495 (2.36); 7.4452 (2.43);7.3056 (1.28); 7.3012 (1.31); 7.2921 (1.71); 7.2875 (2.81); 7.2845(2.71); 7.2731 (2.76); 7.2680 (3.53); 7.2625 (2.17); 72536 (2.00);7.2493 (1.72); 7.1454 (7.99); 7.1256 (9.99); 7.1089 (3.40); 7.1061(3.45); 7.1009 (3.19); 6.3966 (0.62); 6.2112 (0.73); 5.8214 (0.49);5.2873 (0.48); 5.0560 (16.00); 4.0573 (1.05); 4.0395 (2.86); 4.0217(2.89); 4.0039 (1.02); 3.5343 (0.46); 3.5085 (0.64); 3.4613 (5.64);3.4241 (6.71); 3.3750 (2.75); 3.3181 (985.32); 3.2947 (9.68); 3.1905(4.08); 3.1559 (5.82); 3.0106 (5.64); 2.9958 (6.19); 2.9768 (3.91);2.9587 (5.17); 2.6748 (0.71); 2.6702 (0.89); 2.6657 (0.67); 2.6298(0.47); 2.6000 (0.38); 2.5404 (2.13); 2.5100 (52.74); 2.5058 (93.99);2.5014 (119.95); 2.4971 (84.89); 2.3324 (0.52); 2.3281 (0.76); 2.3237(0.53); 2.0692 (0.69); 1.9870 (11.98); 1.9755 (0.47); 1.9086 (1.20);1.7569 (0.88); 1.3749 (0.51); 1.3567 (0.54); 1.2333 (0.90); 1.2227(0.91); 12150 (0.81); 1.2045 (0.94); 1.1931 (3.44); 1.1854 (1.20);1.1753 (6.58); 1:1676 (1.18); 1.1575 (3.27); 0.7769 (0.35); 0.7646(1.10); 0.7545 (0.94); 0.7489 (1.05); 0.7384 (3.36); 0.7282 (4.79);0.7210 (11.03); 0.7061 (3.64); 0.6941 (0.99); 0.6903 (0.97); 0.6798(1.40); 0.6176 (0.32); 0.5831 (1.92); 0.5733 (2.38); 0.5592 (1.60);0.5465 (4.84); 0.5430 (4.80); 0.5141 (0.62); 0.4770 (0.85); 0.4478(4.68); 0.4425 (4.39); 0.4318 (2.02); 0.4213 (2.16); 0.4164 (2.06);0.4061 (1.53); −0.0002 (0.70) Example No. 61 [DMSO—D₆] 7.3205 (1.80);7.3111 (2.00); 7.3056 (0.71); 7.2942 (0.72); 7.2886 (2.17); 6.8850(2.15); 6.8795 (0.72); 6.8680 (0.68); 6.8625 (1.95); 4.9574 (1.80);3.9153 (0.73); 3.8909 (0.81); 3.5097 (1.01); 3.4852 (0.92); 3.3605(0.71); 3.3227 (1.36); 3.3060 (50.00); 2.9857 (0.67); 2.9489 (0.56);2.5098 (4.67); 2.5055 (8.63); 2.5010 (11.29); 2.4966 (8.06); 2.4923(4.02); 1.3981 (5.02); 1.0164 (16.00); −0.0002 (1.24) Example No. 62[DMSO—D₆] 7.6332 (1.86); 7.6280 (0.71); 7.6159 (0.94); 7.6110 (3.76);7.6060 (0.93); 7.5888 (2.29); 7.5808 (0.43); 7.5685 (0.73); 6.8209(0.76); 6.8154 (0.34); 6.8090 (0.36); 6.8012 (2.22); 6.7841 (0.97);6.7786 (2.54); 6.7769 (2.53); 6.7713 (0.91); 6.7595 (0.71); 6.7542(1.82); 6.1347 (2.05); 4.2095 (0.44); 4.0948 (0.47); 4.0663 (0.32);3.7320 (0.40); 3.3051 (57.93); 2.9096 (0.42); 2.8978 (1.91); 2.8939(1.88); 2.8821 (0.42); 2.8261 (0.34); 2.8146 (0.46); 2.7621 (0.50);2.7505 (0.37); 2.5094 (5.71); 2.5052 (10.33); 2.5007 (13.25); 2.4964(9.24); 2.4921 (4.52); 1.3979 (2.76); 1.0494 (16.00); 0.9754 (7.78);−0.0002 (0.94) Example No. 63 [DMSO—D₆] 7.3279 (1.54); 7.1094 (0.95);7.0997 (0.57); 7.0924 (0.63); 7.0871 (1.62); 7.0783 (0.46); 7.0712(0.46); 7.0653 (1.09); 6.8746 (1.19); 6.8684 (0.51); 6.8636 (121);6.8576 (0.63); 6.8517 (0.93); 6.8466 (0.40); 6.8407 (0.86); 4.9299(0.50); 3.8964 (0.75); 3.8722 (0.82); 3.4907 (1.02); 3.4663 (0.93);3.3640 (0.91); 3.3266 (1.80); 3.3030 (58.06); 2.9844 (0.65); 2.9472(0.55); 2.5391 (0.44); 2.5087 (14.42); 2.5044 (25.87); 2.5000 (33.00);2.4957 (23.00); 2.4915 (11.24); 1.9869 (0.38); 1.3984 (1.61); 1.0198(16.00); 0.9829 (4.67); 0.9777 (1.56); 0.9707 (0.75); 0.9098 (0.71);−0.0002 (5.35). Example No. 64 [DMSO—D₆] 8.8354 (1.62); 7.5532 (1.61);7.3063 (1.89); 7.3010 (0.68); 7.2893 (0.72); 7.2840 (2.03); 6.8764(2.07); 6.8710 (0.69); 6.8593 (0.68); 6.8539 (1.84); 4.7224 (1.91);4.0398 (0.49); 4.0220 (0.49); 3.8719 (0.74); 3.8478 (0.81); 3.4267(1.05); 3.4134 (0.75); 3.4026 (0.98); 3.3768 (0.82); 3.3070 (32.70);3.0363 (0.71); 2.9997 (0.60); 2.5096 (3.67); 2.5055 (6.52); 2.5011(8.24); 2.4968 (5.77); 1.9873 (2.06); 1.1932 (0.58); 1.1754 (1.12);1.1577 (0.56); 1.0313 (16.00) Example No. 65 [DMSO—D₆] 7.5754 (0.32);7.3958 (0.37); 7.3564 (1.21); 7.3273 (12.38); 7.3204 (12.61); 7.3051(12.59); 7.0067 (0.69); 7.0003 (0.46); 6.9836 (0.93); 6.9564 (0.82);6.9104 (223); 6.9020 (10.76); 6.8968 (4.74); 6.8848 (4.74); 6.8796(10.18); 6.0874 (2.32); 5.5638 (9.28); 5.5434 (1.03); 4.7445 (2.98);4.7211 (3.94); 4.6845 (0.46); 4.6603 (0.52); 4.6255 (3.25); 4.6022(4.64); 4.5884 (2.33); 4.5425 (2.08); 4.5187 (1.98); 4.4926 (2.27);4.4698 (1.72); 4.4446 (0.53); 4.4214 (1.94); 4.4001 (1.74); 4.3569(0.49); 4.3412 (0.49); 4.3129 (0.39); 42883 (0.42); 4.2817 (0.38);4.2641 (0.59); 4.2527 (0.57); 4.2278 (0.38); 4.2171 (0.48); 4.2022(0.38); 4.0212 (0.35); 3.9865 (0.44); 3.9624 (3.91); 3.9380 (4.36);3.9178 (0.71); 3.7081 (0.44); 3.6826 (0.44); 3.6680 (0.54); 3.6418(0.63); 3.6175 (0.46); 3.5990 (0.69); 3.5711 (0.53); 3.5598 (0.68);3.5053 (4.50); 3.4808 (4.51); 3.4622 (1.42); 3.3888 (6.01); 3.3160(874.85); 3.2956 (74.22); 3.2399 (0.87); 3.0653 (3.66); 3.0283 (2.97);2.6926 (0.35); 2.6742 (0.85); 2.6698 (0.97); 2.6654 (0.86); 2.5051(99.53); 2.5008 (122.29); 2.4967 (92.25); 2.3275 (0.78); 2.0686 (0.80);1.3977 (9.51); 1.3767 (1.02); 1.3686 (1.12); 1.2718 (1.31); 1.2454(0.42); 1.2366 (0.53); 1.0153 (16.00); 0.9394 (0.72); 0.0633 (17.16);0.0527 (33.71); 0.0325 (3.92); −0.0002 (35.52); −0.0208 (3.61); −0.0428(0.81) Example No. 66 [DMSO—D₆] 8.8362 (0.78); 7.5580 (0.79); 7.1042(0.52); 7.0815 (0.85); 7.0600 (0.56); 6.8642 (0.61); 6.8533 (0.61);6.8474 (0.34); 6.8414 (0.51); 6.8305 (0.45); 3.8520 (0.50); 3.8270(0.58); 3.6782 (0.34); 3.5552 (0.72); 3.4101 (4.12); 3.3856 (5.82);3.3296 (9.93); 3.0339 (0.70); 2.9965 (0.57); 2.6735 (0.53); 2.6690(0.65); 2.6644 (0.51); 2.5391 (1.31); 2.5088 (34.34); 2.5044 (61.39);2.5000 (78.29); 2.4956 (54.46); 2.4913 (26.57); 2.3314 (0.40); 2.3268(0.54); 2.3223 (0.41); 2.0692 (0.71); 1.8822 (16.00); 1.0340 (8.50);1.0196 (0.78); 1.0114 (0.38); 0.9893 (0.45); 0.9827 (0.61); −0.0002(3.05 Example No. 67 [DMSO—D₆] 8.8297 (0.42); 8.7997 (5.31); 7.4933(5.67); 7.4784 (0.44); 7.2571 (6.06); 7.2347 (6.57); 7.2262 (0.92);6.9192 (0.61); 6.8976 (0.79); 6.8750 (0.44); 6.8239 (6.22); 6.8015(5.57); 6.7929 (0.67); 5.6795 (0.58); 5.3273 (0.35); 5.3038 (6.42);4.7036 (2.07); 4.6801 (2.60); 4.6098 (0.40); 4.5843 (2.19); 4.5615(3.51); 4.5417 (1.02); 4.4862 (1.28); 4.4610 (1.16); 4.4457 (1.35);4.4238 (0.98); 4.3658 (1.19); 4.3429 (0.99); 4.1534 (0.38); 3.8534(2.44); 3.8293 (2.58); 3.5225 (0.36); 3.5102 (0.39); 3.5034 (0.57);3.4856 (0.41); 3.4438 (0.41); 3.4117 (0.67); 3.3931 (0.86); 3.3619(3.49); 3.3558 (3.78); 3.3276 (4.58); 3.2622 (124.05); 3.0509 (2.43);3.0140 (1.95); 2.4369 (16.00); 1.8446 (0.98); 1.3410 (0.58); 1.2042(0.80); 0.9670 (9.71); 0.8768 (0.46); 0.0194 (0.39); −0.0002 (2.45);−0.0117 (1.54); −0.0666 (1.27) Example No. 69 [DMSO—D₆] 8.3288 (14.89);7.4969 (0.32); 7.4918 (3.25); 7.4880 (1.99); 7.4848 (1.82); 7.4823(2.50); 7.4807 (2.36); 7.4761 (3.72); 7.4701 (0.40); 7.3800 (3.56);7.3760 (2.36); 7.3743 (2.26); 7.3708 (1.85); 7.3677 (2.38); 7.3644(4.46); 7.3587 (0.44); 7.2465 (0.60); 7.2424 (1.26); 7.2343 (4.50);7.2306 (7.33); 7.2248 (9.00); 7.2186 (6.07); 7.2157 (4.20); 7.2071(1.05); 7.2035 (0.48); 7.0884 (16.00); 5.9292 (5.07); 3.6007 (5.10);3.5771 (6.81); 3.4540 (6.59); 3.4303 (4.98); 3.3773 (0.49); 3.3700(0.53); 3.3503 (415.26); 3.3334 (1.13); 3.3267 (2.36); 2.6148 (0.42);2.5241 (0.50); 2.5210 (0.63); 2.5179 (0.68); 2.5090 (22.19); 2.5060(48.42); 2.5030 (66.76); 2.5000 (48.90); 2.4971 (22.85); 2.3872 (0.40);1.3812 (0.41); 1.3647 (1.77); 1.3614 (1.79); 1.3535 (3.30); 1.3442(1.79); 1.3377 (1.70); 0.9547 (1.05); 0.9489 (1.25); 0.9451 (1.94);0.9393 (2.82); 0.9269 (3.81); 0.9237 (3.58); 0.9131 (3.21); 0.9047(2.63); 0.9019 (2.08); 0.8951 (2.54); 0.8885 (3.05); 0.8830 (2.19);0.8716 (2.79); 0.8665 (1.01); 0.8618 (1.51); −0.0002 (5.45 Example No.70 [DMSO—D₆] 7.2936 (0.33); 7.0517 (0.49); 3.5872 (6.83); 3.5664 (8.53);3.5638 (9.10); 3.5536 (16.00); 2.5305 (0.36); 2.5260 (0.74); 2.5214(1.01); 2.5169 (0.75); 2.5125 (0.37); 1.1053 (1.41); 1.0944 (1.49);1.0867 (1.31); 1.0758 (1.22); 0.8895 (1.82) Example No. 71 [DMSO—D₆]8.2670 (2.48); 7.3056 (1.80); 7.3024 (0.58); 7.2949 (0.65); 7.2917(2.28); 7.1687 (1.92); 7.1656 (0.59); 7.1578 (0.55); 7.1548 (1.57);7.0073 (2.58); 5.1235 (2.01); 3.3547 (49.80); 2.6604 (0.34); 2.5108(2.41); 2.5078 (5.23); 2.5048 (7.19); 2.5018 (5.20); 2.4988 (2.38);2.1388 (0.35); 2.1245 (0.41); 2.1038 (0.36); 1.9201 (1.27); 1.9056(1.24); 0.8797 (16.00); −0.0002 (0.84 Example No. 72 [DMSO—D₆] 8.9267(1.91); 7.7250 (2.09); 7.4381 (1.81); 7.4335 (0.60); 7.4218 (0.69);7.4172 (2.04); 7.1304 (1.86); 7.1095 (1.57); 5.2467 (0.91); 3.3164(59.61); 2.6461 (0.35); 2.5240 (0.40); 2.5107 (5.28); 2.5063 (9.71);2.5018 (12.54); 2.4975 (8.57); 2.4931 (4.02); 2.1418 (0.43); 2.0530(0.46); 2.0461 (0.45); 2.0325 (0.66); 2.0269 (0.50); 2.0224 (0.44);2.0143 (0.35); 1.3980 (0.47); 0.9452 (0.34); 0.9358 (1.40); 0.9005(16.00); −0.0002 (1.39) Example No. 73 [DMSO—D₆] 8.9237 (1.78); 7.7117(2.03); 7.0609 (1.47); 7.0393 (1.73); 6.8199 (2.00); 6.8147 (0.66);6.8033 (0.62); 6.7983 (1.64); 5.1982 (1.40); 3.6996 (9.30); 3.3089(285.41); 2.6090 (0.39); 2.6005 (0.38); 2.5394 (0.35); 2.5093 (13.72);2.5049 (25.24); 2.5004 (32.58); 2.4960 (22.37); 2.4916 (10.53); 2.1018(0.32); 2.0911 (0.37); 2.0691 (0.42); 2.0654 (0.43); 2.0370 (0.47);2.0267 (0.38); 1.9985 (0.68); 1.3984 (0.51); 0.8999 (16.00); −0.0002(4.64) Example No. 74 [DMSO—D₆] 8.9279 (1.78); 7.7345 (2.01); 7.2875(0.96); 7.2821 (0.46); 7.2656 (2.44); 7.2401 (1.63); 72186 (0.66);5.2554 (1.51); 3.3026 (49.76); 2.7316 (0.35); 2.7057 (0.33); 2.7002(0.36); 2.6803 (0.35); 2.5094 (5.67); 2.5052 (10.09); 2.5008 (12.78);2.4964 (8.80); 2.4923 (4.21); 2.1767 (0.42); 2.1474 (0.40); 2.1127(0.46); 2.0831 (0.99); 2.0601 (1.10); 1.3983 (0.47); 0.9429 (0.50);0.9053 (16.00); −0.0002 (1.34) Example No. 75 [DMSO—D₆] 8.9410 (2.07);8.9399 (2.07); 8.1363 (1.96); 8.1313 (0.57); 8.1193 (0.62); 8.1143(2.10); 7.7552 (2.06); 7.7538 (2.03); 7.4611 (1.71); 7.4561 (0.53);7.4438 (0.52); 7.4391 (1.61); 5.3387 (2.83); 3.3296 (53.80); 2.5080(7.25); 2.5038 (9.88); 2.5002 (6.49); 22321 (0.45); 2.2066 (0.38);2.1966 (0.39); 2.1238 (0.33); 1.3304 (0.42); 1.0510 (0.39); 0.9522(1.26); 0.9415 (0.33); 0.9075 (16.00); 0.3283 (0.82); −0.0002 (4.08)Example No. 76 [DMSO—D₆] 8.9186 (2.30); 8.9173 (2.19); 7.6869 (2.18);7.6855 (2.09); 6.7899 (1.47); 6.7691 (1.65); 6.4630 (2.02); 6.4581(0.67); 6.4420 (1.78); 5.7549 (0.65); 5.1525 (2.79); 4.7720 (1.54);3.3267 (184.05); 3.1749 (1.34); 3.1618 (1.30); 2.5240 (0.49); 2.5193(0.64); 2.5058 (26.11); 2.5016 (34.99); 2.0270 (0.36); 2.0119 (0.32);2.0043 (0.34); 1.9972 (0.36); 1.9901 (0.39); 1.0259 (0.43); 0.9266(0.38); 0.9189 (1.15); 0.9059 (0.71); 0.8926 (16.00); −0.0002 (4.10)Example No. 77 [DMSO—D₆] 9.8339 (1.22); 8.9443 (1.90); 7.7258 (2.07);7.4431 (1.76); 7.4291 (1.96); 7.0627 (1.68); 7.0487 (1.58); 5.2589(0.38); 4.0336 (0.73); 4.0218 (0.73); 3.3741 (15.42); 2.6125 (0.45);2.6055 (0.36); 2.5099 (9.16); 2.5070 (20.04); 2.5040 (27.74); 2.5010(20.46); 2.4980 (9.44); 2.1854 (0.43); 2.1151 (0.37); 2.1082 (0.39);2.0408 (0.37); 2.0339 (0.37); 2.0186 (0.32); 2.0055 (7.31); 1.9951(0.43); 1.9906 (3.44); 1.9740 (0.35); 1.7368 (0.59); 1.2261 (1.73);1.1862 (0.87); 1.1744 (1.75); 1.1626 (0.86); 1.0530 (0.63); 0.9192(0.61); 0.8978 (16.00); −0.0002 (4.06) Example No. 78 [DMSO—D₆] 8.9301(2.49); 7.7156 (2.28); 7.6926 (0.36); 6.9779 (1.51); 6.9572 (1.91);6.7894 (1.76); 6.7688 (1.45); 5.2144 (2.57); 3.3400 (18.01); 3.3350(32.96); 3.2732 (0.39); 3.2554 (0.36); 2.8710 (1.34); 2.7163 (1.04);2.6244 (0.44); 2.6115 (0.35); 2.5956 (0.34); 2.5853 (0.35); 2.5068(12.22); 2.5026 (16.64); 2.4985 (11.85); 2.1037 (0.32); 2.0923 (0.37);2.0638 (0.39); 2.0376 (0.40); 2.0277 (0.42); 1.9962 (0.34); 1.9894(0.90); 1.3970 (0.34); 1.3296 (0.59); 1.1747 (0.34); 1.1179 (0.83);1.1016 (1.72); 1.0867 (1.61); 1.0842 (1.66); 1.0663 (0.51); 1.0372(0.82); 1.0058 (0.42); 1.0031 (0.53); 0.9209 (0.79); 0.9007 (16.00);0.8645 (0.35); 0.8390 (0.41); 0.8217 (0.35); −0.0002 (2.39) Example No.79 [DMSO—D₆] 8.9167 (1.78); 8.9153 (1.63); 7.7465 (2.03); 7.7450 (1.87);6.9829 (1.43); 6.9782 (0.57); 6.9613 (1.85); 6.8286 (1.97); 6.8235(0.65); 6.8117 (0.61); 6.8068 (1.47); 5.6591 (2.64); 4.3374 (0.82);4.3130 (0.99); 4.1207 (0.99); 4.0962 (0.82); 3.3017 (53.50); 3.2789(0.33); 2.5085 (6.63); 2.5042 (11.78); 2.4998 (14.95); 2.4954 (10.37);2.4911 (4.97); 1.8396 (0.49); 1.3982 (1.80); 1.3565 (1.03); 0.9766(16.00); 0.9482 (0.72); 0.8844 (0.40); 0.8738 (1.01); 0.8686 (1.04);0.8635 (0.52); 0.8583 (0.56); 0.8527 (1.03); 0.8476 (0.96); 0.8374(0.40); 0.5724 (0.44); 0.5621 (1.12); 0.5594 (0.93); 0.5571 (1.12);0.5494 (1.06); 0.5444 (1.06); 0.5335 (0.35); −0.0002 (1.01 Example No.80 [DMSO—D₆] 8.9197 (1.80); 7.7580 (2.14); 7.1388 (1.58); 7.1173 (1.83);6.8575 (1.99); 6.8358 (1.70); 5.6687 (2.61); 4.3497 (0.88); 4.3253(1.07); 4.1348 (1.06); 4.1104 (0.88); 3.3929 (0.56); 3.3754 (0.57);3.3081 (13.07); 2.8941 (0.48); 2.5091 (1.66); 2.5051 (2.96); 2.5007(3.77); 2.4964 (2.66); 1.9760 (0.43); 1.9667 (0.47); 1.9632 (0.48);1.9547 (0.48); 1.9513 (0.50); 1.9484 (0.51); 1.9426 (0.45); 1.7562(0.36); 1.7469 (0.55); 1.7356 (0.73); 1.7266 (0.52); 1.7198 (0.46);1.6362 (0.43); 1.6246 (0.63); 1.6175 (0.63); 1.6054 (0.66); 1.5984(0.34); 1.5946 (0.33); 1.4865 (0.41); 1.4818 (0.41); 1.4722 (0.40);1.4638 (0.50); 1.4582 (0.47); 1.4412 (0.33); 1.4376 (0.32); 1.4345(0.33); 1.3971 (1.81); 1.3587 (0.51); 1.1090 (0.59); 1.0915 (1.16);1.0740 (0.58); 0.9838 (16.00); 0.9655 (3.58) Example No. 81 [DMSO—D₆]9.0400 (1.06); 7.9534 (1.16); 7.6261 (1.10); 7.6209 (0.38); 7.6090(0.42); 7.6038 (1.16); 6.9036 (1.16); 6.8984 (0.40); 6.8865 (0.41);6.8812 (1.09); 6.3895 (1.49); 4.4694 (0.63); 4.4508 (0.68); 3.3067(143.45); 2.5392 (0.44); 2.5090 (11.09); 2.5046 (19.90); 2.5002 (25.31);2.4958 (17.43); 2.4915 (8.32); 1.3985 (16.00); −0.0002 (1.92)

The intensity of sharp signals correlates with the height of the signalsin a printed example of an NMR spectrum in cm and shows the true ratiosof the signal intensities. In the case of broad signals, several peaksor the middle of the signal and their relative intensities may be shownin comparison to the most intense signal in the spectrum. The lists ofthe ¹H NMR peaks are similar to the conventional ¹H NMR printouts andthus usually contain all peaks listed in conventional NMRinterpretations. In addition, like conventional ¹H NMR printouts, theymay show solvent signals, signals of stereoisomers of the targetcompounds, which likewise form part of the subject-matter of theinvention, and/or peaks of impurities. In the reporting of compoundsignals in the delta range of solvents and/or water, our lists of ¹H NMRpeaks show the usual solvent peaks, for example peaks of DMSO in DMSO-D₆and the peak of water, which usually have a high intensity on average.The peaks of stereoisomers of the target compounds and/or peaks ofimpurities usually have a lower intensity on average than the peaks ofthe target compounds (for example with a purity of >90%). Suchstereoisomers and/or impurities may be typical of the particularpreparation process. Their peaks can thus help to identify reproductionof our preparation process with reference to “by-product fingerprints”.An expert calculating the peaks of the target compounds by known methods(MestreC, ACD simulation, but also with empirically evaluated expectedvalues) can, if required, isolate the peaks of the target compounds,optionally using additional intensity filters. This isolation is similarto the relevant peak picking in conventional¹H NMR interpretation.

USE EXAMPLES Example A Sphaerotheca Test (Cucumber)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young cucumberplants are sprayed with the formulation of active ingredient at thestated application rate. 1 day after the treatment, the plants areinoculated with a spore suspension of Sphaerotheca fuliginea. The plantsare then placed in a greenhouse at 70% relative air humidity and atemperature of 23° C. Evaluation follows 7 days after the inoculation.0% means an efficacy which corresponds to that of the control, whereasan efficacy of 100% means that no infection is observed. In this test,the following inventive compounds, at an active ingredient concentrationof 500 ppm, show an efficacy of 70% or more, with the efficienciesobservable in the specific case reported in brackets: 1 (100%), 2 (99%),4 (100%), 5 (100%), 6 (100%), 7 (83%), 8 (94%), 9 (95%), 11 (70%), 12(98%), 14 (95%), 16 (78%), 17 (93%), 18 (95%), 20 (88%), 21 (85%), 22(96%), 23 (80%), 24 (83%), 25 (100%), 26 (75%), 27 (93%), 28 (95%), 29(98%), 31 (100%), 32 (96%), 33 (100%), 34 (99%), 36 (98%), 37 (100%), 38(98%), 39 (100%), 40 (90%), 41 (95%), 42 (94%), 44 (99%), 50 (100%), 51(94%), 52 (100%), 53 (94%), 54 (95%), 57 (100%), 60 (100%), 64 (100%),67 (95%), 72 (100%), 73 (78%), 74 (100%), 79 (93%), 80 (94%).

Example B Venturia Test (Apple)/Protective

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young plants aresprayed with the active ingredient formulation at the stated applicationrate. After the spray coating has dried on, the plants are inoculatedwith an aqueous conidia suspension of the apple scab pathogen Venturiainaequalis and then remain in an incubation cabin at about 20° C. and100% relative air humidity for 1 day. The plants are then placed in agreenhouse at about 21° C. and a relative air humidity of about 90%.Evaluation follows 10 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, whereas an efficacy of 100%means that no infection is observed. In this test, the followinginventive compounds, at an active ingredient concentration of 100 ppm,show an efficacy of 70% or more, with the efficiencies observed in thespecific case reported in brackets: 1 (99%), 2 (93%), 3 (100%), 14(98%), 33 (99%), 41 (95%), 57 (100%), 60 (100%), 79 (100%).

Example C Blumeria graminis Test (Barley)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young plants aresprayed with the formulation of active ingredient at the statedapplication rate. After the spray coating has dried on, the plants aredusted with spores of Blumeria graminis fsp. hordei. The plants areplaced in a greenhouse at a temperature of about 18° C. and a relativeair humidity of about 80% to promote the development of mildew pustules.Evaluation follows 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, whereas an efficacy of 100%means that no infection is observed. In this test, the followinginventive compounds, at an active ingredient concentration of 500 ppm,show an efficacy of 70% or more, with the efficiencies observed in thespecific case reported in brackets: 1 (100%), 2 (100%), 3 (100%), 4(100%), 8 (89%), 11 (78%), 12 (89%), 20 (100%), 33 (89%), 39 (90%), 41(100%), 42 (100%), 53 (94%), 57 (100%), 60 (100%), 79 (100%).

Example D Leptosphaeria Nodorum Test (Wheat)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young plants aresprayed with the formulation of active ingredient at the statedapplication rate. After the spray coating has dried on, the plants aresprayed with spores with a spore suspension of Leptosphaeria nodorum.The plants remain in an incubation cabin at 20° C. and 100% relative airhumidity for 48 hours. The plants are placed in a greenhouse at atemperature of about 22° C. and a relative air humidity of about 80%.Evaluation follows 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, whereas an efficacy of 100%means that no infection is observed. In this test, the followinginventive compounds, at an active ingredient concentration of 500 ppm,show an efficacy of 70% or more, with the efficiencies observed in thespecific case reported in brackets: 1 (100%), 2 (100%), 3 (92%), 4(100%), 12 (86%), 20 (100%), 41 (100%), 53 (83%), 57 (88%), 60 (100%),79 (86%).

Example E Puccinia Triticina Test (Wheat)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young plants aresprayed with the formulation of active ingredient at the statedapplication rate. After the spray coating has dried on, the plants aresprayed with spores with a spore suspension of Puccinia triticina. Theplants remain in an incubation cabin at 20° C. and 100% relative airhumidity for 48 hours. The plants are placed in a greenhouse at atemperature of about 20° C. and a relative air humidity of about 80%.Evaluation follows 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, whereas an efficacy of 100%means that no infection is observed. In this test, the followinginventive compounds, at an active ingredient concentration of 500 ppm,show an efficacy of 70% or more, with the efficiencies observed in thespecific case reported in brackets: 1 (100%), 2 (100%), 3 (89%), 4(100%), 20 (100%), 25 (78%), 33 (83%), 41 (100%), 42 (89%), 53 (100%),60 (95%).

Example F Septoria Tritici Test (Wheat)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the specified amounts ofsolvent and emulsifier, and the concentrate is diluted with water to thedesired concentration. To test for protective activity, young plants aresprayed with the active ingredient formulation at the stated applicationrate. After the spray coating has dried on, the plants are sprayed witha spore suspension of Septoria tritici. The plants remain in anincubation cabin at 20° C. and 100% relative air humidity for 48 hours.Thereafter, the plants are placed under a translucent hood at 15° C. and100% relative air humidity for a further 60 hours. The plants are placedin a greenhouse at a temperature of about 15° C. and a relative airhumidity of 80%. Evaluation follows 21 days after the inoculation. 0%means an efficacy which corresponds to that of the control, whereas anefficacy of 100% means that no infection is observed. In this test, thefollowing inventive compounds, at an active ingredient concentration of500 ppm, show an efficacy of 70% or more, with the efficiencies observedin the specific case reported in brackets: 1 (100%), 2 (100%), 3 (83%),4 (100%), 20 (100%), 25 (86%), 41 (71%), 53 (100%), 57 (70%), 60 (94%),79 (88%).

Example G Fusarium Test (Wheat)/Seed Treatment

The test was conducted under greenhouse conditions. Wheat seeds treatedwith an inventive active compound or a combination of inventive activecompounds were sown in 6×6 cm vessels, into a mixture of steamed fieldsoil and sand (1:1). The test compound(s) were dissolved inN-methyl-2-pyrrolidone and diluted to the desired concentration withwater. Wheat kernels were inoculated with spores of Fusarium culmorum.The infected and ground kernels were distributed between the treatedwheat seeds. The seeds were covered with a top layer of clay granulesand incubated in a greenhouse at 20° C. for 14 days. Evaluation waseffected by counting the plants which emerged. 0% means an efficacywhich corresponds to that of the untreated control, whereas an efficacyof 100% means that all seeds have germinated. In this test, thefollowing inventive compounds exhibit an efficiency of 70% or higher ata dose of 50 g/dt., with the efficiencies observed in the specific casereported in brackets: 1 (100%), 57 (89%), 60 (89%).

Example H Leptosphaeria Test (Oilseed Rape)/Seed Treatment

The test was conducted under greenhouse conditions. Rapeseeds treatedwith an inventive active compound or a combination of inventive activecompounds were sown in 6×6 cm vessels, into a mixture of steamed fieldsoil and to sand (1:1). The test compound(s) were dissolved inN-methyl-2-pyrrolidone and diluted to the desired concentration withwater. Perlite was inoculated with spores of Leptosphaeria maculans. Theinfected perlite was distributed between the treated rapeseeds. Theseeds were covered with a top layer of steamed field soil and sand (1:1)and incubated in a greenhouse at 10° C. for 14 days and at 18° C. for 7days. Evaluation was effected by counting the plants which emerged. 0%means an efficacy which corresponds to that of the untreated control,whereas an efficacy of 100% means that all seeds have germinated. Inthis test, the following inventive compounds exhibit an efficiency of70% or higher at a dose of 50 g/dt., with the efficiencies observed inthe specific case reported in brackets: 1 (70%), 57 (80%), 60 (80%).

Example I Microdochium Test (Wheat)/Seed Treatment

The test was conducted under greenhouse conditions. Wheat seeds treatedwith an inventive active compound or a combination of inventive activecompounds were sown in 6×6 cm vessels, into a mixture of steamed fieldsoil and sand (1:1). The test compound(s) were dissolved inN-methyl-2-pyrrolidone and diluted to the desired concentration withwater. Wheat kernels were inoculated with spores of Microdochium nivale.The infected and ground kernels were distributed between the treatedwheat seeds. The seeds were covered with a top layer of steamed fieldsoil and sand (1:1) and incubated in a greenhouse at 10° C. for 21 days.Evaluation was effected by counting the plants which emerged. 0% meansan efficacy which corresponds to that of the untreated control, whereasan efficacy of 100% means that all seeds have germinated. In this test,the following inventive compounds exhibit an efficiency of 70% or higherat a dose of 50 g/dt., with the efficiencies observed in the specificcase reported in brackets: 57 (78%), 60 (100%).

Example J Rhizoctonia Test (Cotton)/Seed Treatment

The test was conducted under greenhouse conditions. Cottonseeds treatedwith an inventive active compound or a combination of inventive activecompounds were sown in 6×6 cm vessels, into a mixture of steamed fieldsoil and sand (1:1). The test compound(s) were dissolved inN-methyl-2-pyrrolidone and diluted to the desired concentration withwater. Perlite was inoculated with spores of Rhizoctonia solani. Theinfected perlite was distributed between the treated cottonseeds. Theseeds were covered with a top layer of clay granules and incubated in agreenhouse at 20° C. for 7 days. Evaluation was effected by counting theplants which emerged and diseased plants. 0% means an efficacy whichcorresponds to that of the untreated control, whereas an efficacy of100% means that all seeds have germinated and all plants are healthy. Inthis test, the following inventive compounds exhibit an efficiency of70% or higher at a dose of 50 g/dt., with the efficiencies observed inthe specific case reported in brackets: 1 (70%), 57 (80%), 60 (90%).

Example K Pyricularia Test (Rice)/Protective

Solvent: 28.5 parts by weight of acetoneEmulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with waterand the stated amount of emulsifier. To test for protective activity,young rice plants are sprayed with the formulation of active ingredientat the stated application rate. 1 day after the treatment, the plantsare inoculated with an aqueous spore suspension of Pyricularia oryzae.The plants are then placed in a greenhouse at 100% relative air humidityand a temperature of 25° C. Evaluation follows 5 days after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, whereas an efficacy of 100% means that no infection isobserved. In this test, the following inventive compounds show, at anactive ingredient concentration of 250 ppm, an efficacy of 80% or more:1, 57, 60.

Example L Rhizoctonia Test (Rice)/Protective

Solvent: 28.5 parts by weight of acetoneEmulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with waterand the stated amount of emulsifier. To test for protective activity,young rice plants are sprayed with the formulation of active ingredientat the stated application rate. 1 day after the treatment, the plantsare inoculated with hyphae of Rhizoctonia solani. The plants are thenplaced in a greenhouse at 100% relative air humidity and a temperatureof 25° C. Evaluation follows 4 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed. In this test, the followinginventive compounds show, at an active ingredient concentration of 250ppm, an efficacy of 80% or more: 57, 60.

Example M Cochliobolus Test (Rice)/Protective

Solvent: 28.5 parts by weight of acetoneEmulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with waterand the stated amount of emulsifier. To test for protective activity,young rice plants are sprayed with the formulation of active ingredientat the stated application rate. 1 day after the treatment, the plantsare inoculated with an aqueous spore suspension of Cochliobolusmiyabeams. The plants are then placed in a greenhouse at 100% relativeair humidity and a temperature of 25° C. Evaluation follows 4 days afterthe inoculation. 0% means an efficacy which corresponds to that of thecontrol, whereas an efficacy of 100% means that no infection isobserved. In this test, the following inventive compounds show, at anactive ingredient concentration of 250 ppm, an efficacy of 80% or more:1, 57, 60.

Example N Phakopsora Test (Soya Beans)/Protective

Solvent: 28.5 parts by weight of acetoneEmulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with waterand the stated amount of emulsifier. To test for protective activity,young plants are sprayed with the formulation of active ingredient atthe stated application rate. 1 day after the treatment, the plants areinoculated with an aqueous spore suspension of Phakopsora pachyrhizi.The plants are then placed in a greenhouse at 80% relative air humidityand a temperature of 20° C. Evaluation follows 1 day after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, whereas an efficacy of 100% means that no infection isobserved. In this test, the following inventive compounds show, at anactive ingredient concentration of 250 ppm, an efficacy of 80% or more:1, 57.

1. A compound of formula (I)

in which X is O or S, Y is O, —CH₂— or a direct bond, m is 0 or 1, n is0 or 1, R is alkyl, alkenyl, cycloalkyl or aryl, each of which isoptionally substituted, R¹ is hydrogen, SH, alkylthio, alkoxy, halogen,haloalkyl, haloalkylthio, haloalkoxy, cyano, nitro or Si(alkyl)₃, A isphenyl or naphthyl, each of which is substituted with one Z, Z ishalogen, cyano, nitro, OH, SH, C(alkyl)(═NOalkyl), C₃-C₇-cycloalkyl,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₁-C₄-alkylsulphinyl,C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, formyl, C₂-C₅-alkylcarbonyl,C₂-C₅-haloalkylcarbonyl, C₂-C₅-alkoxycarbonyl, C₂-C₅-haloalkoxycarbonyl,C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₂-C₅-alkylcarbonyloxy,C₂-C₅-haloalkylcarbonyloxy, trialkylsilyl, or phenyl, phenoxy orphenylthio, each of which is optionally monosubstituted with halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄alkoxy or C₂-C₄alkylcarbonyl, andsalts thereof, with the proviso that if Y is O, m is 0, n is 0, R istert-butyl, and R¹ is hydrogen, then A is not chlorophenyl or4-methylphenyl.
 2. The compound of claim 1, in which X is S, Y is O,—CH₂— or a direct bond, m is 0 or 1, n is 0 or 1, R is optionallybranched C₃-C₇-alkyl, optionally branched C₁-C₈-haloalkyl, optionallybranched C₂-C₇-alkenyl, optionally branched C₂-C₇-haloalkenyl, C₃-C₇cycloalkyl which is optionally substituted with halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio orC₁-C₄-alkylthio, or phenyl which is optionally substituted withmono-halogen, di-halogen, tri-halogen, or C₁-C₄-alkyl, R¹ is hydrogen,SH, C₁-C₄-alkylthio, C₁-C₄-alkoxy or halogen, A is phenyl, which issubstituted with one Z, Z is halogen, cyano, nitro,C(C₁-C₅-alkyl)(═NO(C₁-C₅-alkyl)), C₃-C₆-cycloalkyl, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₂-C₅-alkylcarbonyl, C₂-C₅-alkoxycarbonyl,C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₂-C₅-alkylcarbonyloxy, or phenyl,phenoxy or phenylthio, each of which is monosubstituted with halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₂-C₄-alkylcarbonyl.
 3. Amethod for controlling phytopathogenic harmful fungi, comprisingapplying a compound of claim 1 to the phytopathogenic harmful fungi,their habitat, or combinations thereof.
 4. A composition for controllingphytopathogenic harmful fungi, comprising the compound of claim 1 and anextender, a surfactant, or combinations thereof.
 5. The composition ofclaim 4, further comprising at least one further active ingredientselected from the group consisting of insecticides, attractants,sterilants, bactericides, acaricides, nematicides, fungicides, growthregulators, herbicides, fertilizers, safeners, semiochemicals, andcombinations thereof.
 6. (canceled)
 7. A method of inhibiting vegetativegrowth comprising applying the compound according to claim 1 to seed, aplant, parts of a plant, fruit of a plant, soil surrounding a plant, orcombinations thereof.
 8. A process for producing the composition ofclaim 4, comprising mixing the compound of claim 1 with an extender, asurfactant, or combinations thereof.
 9. The method according to claim 7,wherein the plant is a transgenic plant.
 10. The method according toclaim 7, wherein the seed is from a transgenic plant.
 11. The compoundof formula (VIII-a)

in which X is O or S, R^(a) is alkyl, alkenyl, cycloalkyl or aryl, eachof which is optionally substituted, with the proviso that when X is S,R^(a) is not tert-butyl.
 12. A method of promoting vegetative growthcomprising applying the compound according to claim 1 to seed, a plant,parts of a plant, fruit of a plant, soil surrounding a plant, orcombinations thereof.
 13. The compound of claim 1, wherein X is S, Y isO or a direct bond, m is 0, n is 0 or 1, R is tert-butyl, isopropyl,1,3-difluoro-2-methylpropan-2-yl, 1-chlorocyclopropyl,1-fluorocyclopropyl, 1-methylcyclopropyl, 1-methylcyclohexyl,(3E)-4-chloro-2-methylbut-3-en-2-yl, triisopropylsilyl, or1-(trifluoromethyl)cyclopropyl, R¹ is hydrogen, halogen, Si(alkyl)₃, orSH, A is phenyl, and Z is selected from the group consisting of halogen,nitro, C(alkyl)(═NOalkyl), C₃-C₇-cycloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, or phenyl which is optionallysubstituted with halogen, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, orC₂-C₄-alkylcarbonyl.